Fungicidal triazoles and imidazoles

ABSTRACT

Substituted silylmethyl 1,2,4-triazoles and imidazoles also having selected substituents on the heterocyclic ring, agriculturally useful compositions comprising such compounds and the use of such compounds as fungicides.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of my copending application U.S. Ser. No. 855,297 filed Apr. 24, 1986, now abandoned.

BACKGROUND OF THE INVENTION

U.S. Pat. No. 4,510,136 issued on Apr. 9, 1985 to W. K. Moberg claims 1,2,4-triazole derivatives of the following formula: ##STR1## and their use as fungicides. The substitutent groups, Q₁ and Q₂, are limited to H or CH₃.

U.S. Pat. No. 4,530,922 issued on July 23, 1985 to W. K. Moberg discloses fungicidal imidazoles and triazoles containing silicon of the following formula: ##STR2##

The A group in the ring is limited to CH or N.

U.S. Pat. No. 3,692,798 discloses compounds of the formula: ##STR3## wherein

R₁, R₂ and R₃ can be lower alkyl and phenyl. It is stated that these compounds are useful as antimicrobial agents.

U.S.S.R. Pat. No. 346,306 discloses silylmethylazoles of the formula:

    (R.sub.1).sub.n (R.sub.2 O).sub.3-n SiCH.sub.2 Az

wherein R₁ and R₂ are alkyl groups, n is 0-3, and Az is a pyrazole, imidazole, or benzimidazole ring, optionally substituted.

European Pat. No. 11,769 teaches that compounds of the general formula: ##STR4## wherein R is a substituted phenyl, naphthyl or tetrahydronaphthyl ring;

R₁ is a substituted phenyl or cycloalkyl ring;

R₂ is H, or together with R₁ it may form an annelated aryl or alkyl ring;

R₃ is halogen, alkyl, alkoxy or haloalkyl;

n is 0, 1, 2 or 3; and

X is CH or N,

are useful as antimicrobial agents.

European Pat. No. 15,756 discloses compounds of the formula: ##STR5## wherein R₁ is alkyl, cycloalkyl, or substituted phenyl; and

R₂ is substituted phenyl or benzyl,

and their use as agricultural fungicides.

European Pat. No. 36,153 discloses compounds of the formula: ##STR6## wherein R₁, R₂ and R₃ are H or Cl, provided that at least one of R₁ or R₃ is Cl,

and their use as antimicrobials.

Belgian Pat. No. 867,245 discloses compounds of the formula: ##STR7## wherein Z is aryl;

R₁ is CN, H, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, substituted aryl, or substituted aralkyl;

R₂ is H, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, substituted aryl, substituted aralkyl, alkoxy, alkenoxy, alkynoxy, OH, substituted aryloxy, or substituted aralkyloxy;

m is 0 or 1; and

n is 1 or 2,

and their use as agricultural fungicides.

U.S. Pat. No. 4,414,210 discloses compounds of the formula: ##STR8## wherein Z is an aryl or substituted aryl group;

R₁, R₂, and R₃ are independently H, CN, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, substituted aryl, aralkyl, or substituted aralkyl; and

W is a 1- or 4-(1,2,4-triazole),

and their use as agricultural fungicides.

SUMMARY OF THE INVENTION

This invention pertains to silylmethyl triazoles and imidazoles, having the formula ##STR9## to compositions containing such triazoles or imidazoles, and to their use as fungicides.

In the formula

R₁ is ##STR10## naphthyl, --CR₇ ═CHR₈, or --C.tbd.CR₇ ; R₂ and R₃ are independently C₁ -C₆ alkyl, vinyl, CH₂ CR₉ ═CR₁₀ R₁₁, ##STR11## or OR₁₂ provided that both R₂ and R₃ may not be OR₁₂ ;

R₄ is H or CH₃ ;

R₅ and R₆ are independently H, F, Cl, Br, OCH₃, SCH₃, OCF₂ H, OCF₃, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, phenyl, or halophenyl;

R₇ and R₈ are independently H, C₁ -C₄ alkyl; or ##STR12## R₉, R₁₀ and R₁₁ are independently H or CH₃ : X is H, C₂ -C₄ alkenyl, ethynyl, F, Cl, Br, I, NO₂, SH and its corresponding disulfide, SeH and its corresponding diselenide, ##STR13## Y is H, F, Cl, Br, I, ##STR14## SSR₁₇, CO₂ CH₃, CHO, or SH and its corresponding disulfide;

Z is CH or N;

m is 0 or 1;

n is 0, 1, or 2;

R₁₂ is H or C₁ -C₄ alkyl;

R₁₃ is H, C₁ -C₄ alkyl, allyl, benzyl, C₁ -C₄ alkylcarbonyl, C₁ -C₄ haloalkylcarbonyl;

R₁₄ and R₁₅ are independently H, C₁ -C₄ alkyl, allyl, benzyl, or phenyl optionally substituted with 1-3 substituents independently selected from halogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, NO₂ or SCH₃ ;

R₁₆ is H, C₁ -C₈ alkyl, C₃ -C₈ cycloalkyl, C₂ -C₈ alkenyl, C₄ -C₈ cycloalkenyl, alpha-pinenyl, aralkyl, aralkenyl, or phenyl optionally substituted with 1-3 substituents independently selected from halogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, NO₂ or SCH₃ ;

R₁₇ is C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, allyl, benzyl or phenyl optionally substituted with 1-3 substituents independently selected from halogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, NO₂ or SCH₃ ;

R₁₈ is C₁ -C₅ alkyl, C₁ -C₄ haloalkyl, CH₂ SCN, C₂ -C₄ alkenyl, CHR₉ (CHR₁₀)_(m) CN, CH₂ CO₂ R₁₄, C₃ -C₄ alkynyl, CH₂ NO₂, benzyl, CH₂ OCH₃, ##STR15## R₁₉ is CH₃, phenyl, or benzyl; R₂₀ is C₁ -C₄ alkyl, CH₂ CN, CH₂ SCN, or allyl;

R₂₁ is C₂ -C₄ alkyl, CH₂ CN, or CH₂ SCN;

provided that: (1) either X or Y must be H, but both X and Y cannot be H simultaneously; and (2) when Z is CH, then Y is H and X is S(O)_(n) R₂₁, SO₂ OH, I or SH and its corresponding disulfide.

Preferred

Preferred for their high fungicidal activity, or their ease of synthesis, or both, are compounds wherein ##STR16## R₅ and R₆ are independently H, F, Cl, Br, phenyl, or halophenyl; R₂ is C₁ -C₄ alkyl or ##STR17## R₃ is C₁ -C₄ alkyl, vinyl, allyl, or OR₁₂ ; R₄ is H;

X is F, Cl, I, ##STR18## SSR₁₇, or SH and its corresponding disulfide; and Y is H.

More preferred are compounds wherein

R₃ is C₁ -C₄ alkyl, allyl, or OR₁₂ ;

R₅ and R₆ are independently H, F, Cl, Br, phenyl, or halophenyl substituted at the 4-position; and

X is I, ##STR19## SSR₁₇, or SH and its corresponding disulfide.

Most preferred are compounds wherein X is I, ##STR20## SSR₁₇, or SH and its corresponding disulfide.

Specifically preferred for reasons of greatest ease of synthesis or highest fungicidal activity or both are:

1. 1-[bis(4-fluorophenyl)(methyl)silylmethyl]-1H-1,2,4-triazole-5-thiol;

2. 1-[bis(4-fluorophenyl)(methyl)silylmethyl]-5-iodo-1H-1,2,4-triazole;

3. 1-[bis(4-fluorophenyl)(methyl)silylmethyl]-5-(cyanomethylsulfonyl)-1H-1,2,4-triazole; and

4. 1-[bis(4-fluorophenyl)(methyl)silylmethyl]-2-iodo-1H-imidazole.

DETAILED DESCRIPTION OF THE INVENTION Synthesis

I. Synthesis of 1,5-Disubstituted-1,2,4-Triazoles

The compounds of Formula Ia, in which Y is H, can be prepared from compounds of Formula II by the methods described below. ##STR21## Compounds of Formula II can be prepared by various methods, as disclosed in U.S. Pat. Nos. 4,510,136 and 4,530,922.

A. Metalation and Subsequent Functionalization

The metalation of II with strong bases (Equation 1) provides the 5-metalated triazoles III (R. G. Micetich et al., Heterocycles 1985, 23, 1645-49).

Equation 1 ##STR22##

Suitable bases include organoalkali metal compounds, such as n-butyllithium, and alkali metal amides, such as lithium diisopropylamide. Appropriate solvents for the metalation include hydrocarbons such as toluene, and ethereal solvents such as tetrahydrofuran (THF), dimethoxyethane (DME) and diethyl ether. The metalations can be carried out from -80° C. to 60° C. for periods of 1 to 120 minutes, depending on the choice of base, solvent and substrate. Typical conditions involve treatment of a solution of II in THF at -70° C. with n-butyllithium for 15 minutes, which gives III where the metal is lithium. When R₂ or R₃ is OH, two equivalents of base are required.

Other methods for the preparation of organo-metallic compounds which are known to one skilled in the art are applicable to the preparation of III, and include halogen-metal exchange between halotriazoles and organometallic compounds, reductive metalation of halotriazoles and the reaction of III with anhydrous metal salts. For a review, see J. March. Advanced Organic Chemistry, 3rd Edition, J. Wiley and Sons, New York, N.Y., 1985, p. 1169-1170.

The use of organometallic compounds of Formula III in appending a wide variety of functional groups to metalated carbon centers has been reviewed (H. G. Gschwend and H. R. Rodriguez, Organic Reactions, Volume 26, W. G. Dauben, Ed., J. Wiley and Sons, New York, N.Y., 1979, p. 1; J. March, op. cit., see Index under Grignard reagents, p. 1314). More specifically, transformations of III to compounds of this invention are discussed below according to the type of bond formed to C-5 of the triazole ring.

Metalation of a 1-substituted imidazole, by analogy to Equation 1 above, yields a 2-metalated imidazole analogous to the compound of Formula III. Subsequent treatment according to the methods described for triazoles provides 1,2-disubstituted imidazoles analogous to the compounds of Formula Ia.

1. Bonds to Carbon

The conversion of compounds of Formula III to compounds of this invention having C-5 carbon bonds is outlined in Scheme I and involves standard transformations known to one skilled in the art. Some examples are given below.

Scheme I ##STR23##

The reaction of compounds of Formula III with acid derivatives such as dialkylamides provides acyltriazoles V (S. Ohta et. al., Heterocycles 1985, 23, 1759-64).

Treatment of III with CO₂, COS or CS₂ provides the metal salts of the 5-triazole carboxylic acids, thioacids and dithioacids. In some cases, the parent carboxylic acids readily decarboxylate. (Micetich, op.cit.). Alkylation of these metal salts with, for example, non-aryl R₁₄ iodides in methyl ethyl ketone or THF provides esters, thioesters or dithioesters of Formula VI. These esters are precursors of VI where R₁₄ constitutes an aryl group, via exchange reactions of R₁₄ OH or R₁₄ SH under the influence of basic or acidic catalysis.

The 5-formyltriazoles of Formula V are intermediates for the preparation of other C-5 carbon bond compounds of this invention using methods known to one skilled in the art, as shown in Scheme II. For example, the reaction of 5-formyltriazoles with dibromomethylenetriphenylphosphorane provides dibromoolefins VIII (W=Br) which may be converted to alkynes of Formula IX using n-butyllithium (E. J. Corey et al., Tetrahedron Lett. 1972, 3769).

Scheme II ##STR24##

2. Bonds to Sulfur or Selenium

The conversion of compounds of Formula III to mercaptan metal salts or mercaptans X (X=SH) can be carried out using standard procedures (see March, op. cit., p. 550). These can be converted to other compounds of this invention having C-5 sulfur bonds following procedures known to one skilled in the art, as shown in Scheme III. For example, disulfides of Formula XIV can be prepared by treatment of thiols X with sulfenyl chlorides or phthalimidosulfides in inert solvents (D. N. Harpp et al., Tetrahedron Lett. 1970, 3551). Sulfenamides of Formula XIII are available by the reaction of disulfides XII with lithium dialkylamides (H. Ikehira et al., Synthesis 1983, 716) and by treatment of sulfenyl halides with amines (R. Lejeune et al., J. Pharm. Belg. 1984, 39, 217). ##STR25##

Sulfides of Formula XI can be converted to sulfoxides and sulfones using standard procedures.

The selenides and selenoxides of the present invention can be prepared using methods similar to those employed for the preparation of sulfides of Formula XI and corresponding sulfoxides.

The thiols of Formula X are precursors to other C-5 sulfur substituted compounds of this invention as shown in Scheme IV. For example, treatment of thiols X with cyanogen halides provides thiocyanates of Formula XV (C. Temple and J. A. Montgomery, Triazoles, Vol. 37 of Heterocyclic Compounds, A. Weissberger and E. C. Taylor, Eds., J. Wiley and Sons, New York, N.Y., 1981, p. 257). Treatment of X with R₁₄ NCY (Y=O or S) provides thiocarbamates XVI (ibid.). ##STR26##

3. Bonds to Other Elements

The preparation of 5-halotriazoles of Formula Ia can be carried out using methods known to one skilled in the art (see Gschwend, op. cit., p. 83 and March, op. cit., p. 551). For example, treatment of III, where the metal is lithium, with iodine provides Ia where X is iodine (Equation 2).

Equation 2 ##STR27##

Treatment of III in ethereal solvents such as THF with R₁₅ O(R₁₄ O)P(Cl)O where R₁₅, R₁₄ ≠H gives C-5 phosphates. Treatment with iodotrimethylsilane, then water, where R₁₅, R₁₄ are n-alkyl or benzyl, gives the C-5 phosphonic acids.

Amination of III can be carried out using CH₃ ONHR₁₂ (March, op. cit., p. 553). Alternatively, III can be reacted with an arenesulfonyl azide, followed by reduction with, e.g., NaBH₄ (J. N. Reed and V. Snieckus, Tetrahedron Lett. 1983, 24, 3795). The resulting amines can be alkylated or oxidized to compounds where X=NO₂ using methods known to one skilled in the art.

B. Other Methods

Compounds of the present invention where X=NR₉ NR₁₂ R₁₄ are available by the reaction of, for example, the 5-bromotriazoles with hydrazines (Temple and Montgomery, Triazoles, op. cit., p. 291).

Compounds of Formula II react with sulfenyl halides, such as perchloromethylmercaptan in inert solvents such as methylene chloride, in the presence of triethylamine to give sulfides of Formula XI.

II. Synthesis of 1,3-Disubstituted-1,2,4-Triazoles

The compounds of Formula Ib in which X is H, can be prepared by alkylation of silylmethyl halides XXII or sulfonate esters with metal salts of Z¹ -substituted triazoles, where Z¹ is Y or can be converted to Y using known procedures. Examples of ##STR28## Z¹ to Y conversions are given in Section I: Synthesis of 1,5-Disubstituted-1,2,4-Triazoles. It is understood that with this procedure, mixtures of 1,3- and 1,5-disubstituted-1,2,4-triazoles may be produced, from which the desired isomers can be isolated using standard techniques.

A variety of substituted triazoles are available using literature procedures (Temple and Montgomery, Triazoles, op. cit., see Index). Alkylation of halomethylsilanes as described in U.S. Pat. Nos. 4,510,136 and 4,530,922 with Z¹ -substituted triazoles, where Z¹ is Y or can be converted to Y using standard procedures, provides silylmethyl-(Z¹ -substituted) triazoles. For example, 1,2,4-triazole-3-thiol can be alkylated with trityl chloride (T. W. Greene, Protective Groups in Organic Synthesis, J. Wiley and Sons, New York, N.Y., 1981, p. 201). The potassium salt of the resulting tritylthiotriazole can be allowed to react with halomethylsilanes and the product deprotected (Greene, loc. cit.) (Equation 3). The 3-mercaptotriazole XX can be converted to other compounds of Formula Ib having C-3 sulfur bonds.

Equation 3 ##STR29##

Similarly, alkylation of halomethylsilanes with a metal (e.g., potassium) salt of 3-nitro-1,2,4-triazole provides the analogous 3-nitro-1-silylmethyltriazole, which can be reduced to give the 3-amino compound.

Similar reactions are possible for other values of Z¹ (X, Y), and in many cases no protection-deprotection is required. Depending on Z¹ (X, Y) and the reaction conditions used, varying amounts of 5-substituted 1-silylmethyltriazoles may also be prepared. The 3- and 5-substituted triazoles may be separated by standard methods, such as chromotography.

In the following examples, temperatures are reported in degrees Celsius. Abbreviations for nuclear magnetic resonance (nmr) spectra are s=singlet, d=doublet, t=triplet, q=quartet, m=multiplet, br=broad; peak positions are reported as parts per million downfield from tetramethylsilane. Hexanes refers to a mixture of isomers boiling from 68°-69° and ether refers to diethyl ether. All reactions involving organo-metallic reagents or metal hydrides were run under an atmosphere of dry nitrogen. "Flash" chromatography refers to the method described by Still et al. (J. Org. Chem. (1978) 43, 2923).

EXAMPLE 1 Metalation of 1-Silylmethyl-1,2,4-triazoles Preparation of bis(4-Fluorophenyl)methyl[5-(3-phenylpropen-1-ol)-1H-1,2,4-triazol-1-ylmethyl]silane

To a solution of 3.2 g (0.010 mol) of bis(4-fluorophenyl)methyl(1H-1,2,4-triazol-1-ylmethyl)silane in 15 mL of THF cooled to -78° was added 6.5 mL (0.010 mol) of 1.6M n-butyllithium in hexane over 3 minutes. After 15 minutes, 1.3 g (0.010 mol) of cinnamaldehyde was added and the solution was stirred 30 minutes. Saturated aqueous NH₄ Cl was added and the mixture was extracted with 1:1 ether/hexanes. The organic extracts were washed with brine, dried over MgSO₄ and evaporated. The crude product was flash chromatographed using 10% ether/methylene chloride to give 3.5 g of the title compound as a viscous glass: ir (neat) 3400-3000 (br), 1900, 1585, 1490, 1100, 965 cm⁻¹ ; nmr (CDCl₃) δ 0.7 (3H, s), 3.5 (1H, br s), 4.2 (2H, s), 5.4 (1H, d, J=6 Hz), 6.2 (1H, dd, J=16, 6 Hz), 6.6 (1H, d, J=16 Hz), 7.0 (4H, m), 7.3 (5H, s), 7.4 (4H, m), 7.8 (1H, s).

EXAMPLE 2 Preparation of bis(4-Fluorophenyl)methyl(5-formyl-1H-1,2,4-triazol-1-ylmethyl)silane

Bis(4-fluorophenyl)methyl(1H-1,2,4-triazol-1-ylmethyl)silane (1.3 g, 0.004 mol) was lithiated as described in Example 1 using 3.7 mL (0.0044 mol) of 1.2M n-butyllithium in 10 mL of THF. DMF (1.2 mL, 0.016 mol) was added and the solution was allowed to warm to 0° C. After 1 hour, the reaction mixture was diluted with 1:1 ether/hexanes, washed with 7% aqueous NaHCO₃ and brine, dried over Na₂ SO₄ and evaporated. Flash chromatography using 10% ether/methylene chloride gave 1.1 g of the title compound as a clear oil: n^(D) 1.5612; ir (neat) 2840, 1705, 1587, 1499, 1228, 1160, 1106, 821 cm⁻¹ ; nmr (CDCl₃) δ, 0.7 (3H, s), 4.7 (2H, s), 7.0 (4H, t), 7.4 (4H, m), 7.9 (1H, s), 9.8 (1H, s).

EXAMPLE 3 Oxidation of Alcohols IV Preparation of bis(4-Fluorophenyl)methyl[5-(2,5-dimethylbenzoyl)-1H-1,2,4-triazol-1-ylmethyl]silane

To a mixture of 1.5 g (0.0033 mol) of bis(4-fluorophenyl)methyl[5-(2,5-dimethylphenyl)hydroxymethyl-1H-1,2,4-triazol-1-ylmethyl]silane and 2.2 g of Celite in 20 mL of CH₂ Cl₂ was added 1.1 g (0.005 mol) of pyridinium chlorochromate. The mixture was stirred overnight, filtered and evaporated, leaving a dark residue. Flash chromatography (CH₂ Cl₂) gave 1.2 g of the title compound as a yellow oil: ir (neat) 2940, 1665, 1595, 1505, 1240, 1170, 1118, 950, 830 cm⁻¹ ; nmr (CDCl₃) δ 0.8 (3H, s), 2.30 (6H, s), 4.9 (2H, s), 7.0-7.3 (7H, m), 7.5 (4H, t), 7.9 (1H, s).

EXAMPLE 4 Preparation of bis(4-Fluorophenyl)methyl(5-methylthiocarbonyl-1H-1,2,4-triazol-1-ylmethyl)silane

To a -78° C. solution of 0.016 mol of lithio[bis(4-fluorophenyl)methyl(1H-1,2,4-triazol-1-ylmethyl)silane, prepared in 75 mL of THF as described in Example 1, was added 1 mL of liquid carbonyl sulfide. The solution was allowed to warm to 0° over 1 hour, and 1.0 mL (0.016 mol) of iodomethane was added. The reaction mixture was stored at 25° for 3 days, then poured into saturated aqueous NH₄ Cl. The aqueous layer was extracted twice with ether, and the combined organic layers were dried (MgSO₄) and evaporated to give 5.2 g of the title compound as a yellow oil: n^(D) 1.5694; ir (neat) 1710 (w), 1663; nmr (CDCl₃) δ 0.7 (3H, s), 2.3 (3H, s), 4.6 (2H, s), 7.0 (4H, m), 7.4 (4H, m), 7.8 (1H, s).

EXAMPLE 5 Preparation of bis(4-Fluorophenyl)methyl(5-iodo-1H-1,2,4-triazol-1-ylmethyl)silane

A solution of 3.14 g (0.010 mol) of bis(4-fluorophenyl)methyl(1H-1,2,4-triazol-1-ylmethyl)silane in 15 ml of THF was lithiated as described in Example 1, using 7.1 ml (0.011 mol) of 1.55M n-butyllithium in hexane. To this solution was added 1.4 g (0.011 mol) of iodine. The reaction mixture was allowed to warm to 0°, stirred 3 hours, poured into 1:1 ether/hexanes, washed with 7% aqueous NaHCO₃ and brine, dried over Na₂ SO₄, filtered and evaporated. The crude product was flash chromatographed (5% ether/methylene chloride) to give 0.83 g of the title compound as a white solid: m.p. 102°-104°; nmr (CDCl₃) δ 0.7 (3H, s), 4.2 (2H, s), 7.1 (4H, m), 7.5 (4H, m), 7.8 (1H, s).

EXAMPLE 6 Preparation of bis(4-Fluorophenyl)methyl(5-methylthio-1H-1,2,4-triazol-1-ylmethyl)silane

A solution of 1.5 g (0.005 mol) of bis(4-fluorophenyl)methyl(1H-1,2,4-triazol-1-ylmethyl)silane in 10 mL of THF was treated with n-butyllithium as described in Example 1. To this solution was added 0.63 mL (0.007 mol) of dimethyl disulfide. The reaction mixture was allowed to warm to 0°, stirred 30 minutes, then poured into 1:1 ether/hexanes, washed with 7% aqueous NaHCO₃ and brine, dried over Na₂ SO₄, filtered and evaporated. The crude product was flash chromatographed (5% ether/methylene chloride) to give 1.4 g of the title compound as a clear oil: n^(D) 1.5750; ir (neat) 3030 (w), 2935 (w), 1587, 1496, 1230, 1160, 1106, 1035, 822 cm⁻¹ ; nmr (CDCl₃) δ 0.7 (3H, s), 2.6 (3H, s), 4.0 (2H, s), 7.1 (4H, m), 7.5 (4H, m), 7.8 (1 H, s).

EXAMPLE 7 PREPARATION of bis(4-Fluorophenyl)methyl(5-mercapto-1H-1,2,4-triazol-1-ylmethyl)silane

To a solution of 134 g (0.424 mol) of bis(4-fluorophenyl)methyl(1H-1,2,4-triazol-1-ylmethyl)silane in 850 mL of THF cooled to -70° was added 265 mL (0.424 mol) of 1.6M n-butyllithium in hexane over 15 minutes, keeping the temperature below -60°. After 20 minutes, 13.6 g (0.424 mol) of sulfur was added all at once. The reaction mixture was allowed to warm to 0° over 1 hour, during which time the sulfur was taken up, then the reaction mixture was brought to pH 1 with 475 mL of 1N HCl. The aqueous layer was extracted with ether and the combined organic layers were washed with brine, dried over Na₂ SO₄ and evaporated to a light orange oil. This was taken up in 150 mL of hot 1:9 benzene/cyclohexane. Cooling, seeding with crystals produced by ether trituration, and filtration gave 104 g of the title compound as ivory crystals: m.p. 97°-99°; ir (nujol) 3030 (br), 1578, 1222, 1150, 1098, 951, 813 cm⁻¹ ; nmr (CDCl₃) δ 0.7 (3H, s), 4.2 (2H, s), 7.0 (4H, t), 7.5 (4H, m), 7.6 (1H, s), 12.0 (1H, br s).

The filtrate was diluted with cyclohexane and allowed to stand at 25°. A second crop of 15 g of less pure material was collected.

EXAMPLE 8 Preparation of bis(4-Fluorophenyl)methyl[5-(thiocyanatomethylthio)-1H-1,2,4-triazol-1-ylmethyl]silane

A -78° solution of 0.010 mol of lithio-[bis(4-fluorophenyl)methyl(1H-1,2,4-triazol-1-ylmethyl)silane] in 15 mL of THF, prepared as described in Example 1, was treated with 0.32 g (0.010 mol) of sulfur, allowed to warm to 25° over 1 hour, then cooled to -78° and treated with 0.86 mL (0.011 mol) of chloromethylthiocyanate. The reaction mixture was allowed to warm to 25° C. and was stirred 3 hours, then poured into 1:1 ether/hexanes and 7% aqueous NaHCO₃. The aqueous layer was extracted with 1:1 ether/hexanes and the combined organic layers were washed with brine, dried over Na₂ SO₄ and evaporated. Flash chromatography using 2-20% ether/methylene chloride gave 2.7 g of the title compound as an oil: ir (neat) 3010, 2155, 1590, 1499, 1230, 1163, 1109, 1040, 825 cm⁻¹ ; nmr (CDCl₃) δ 0.7 (3H, s), 4.0 (2H, s), 4.6 (2H, s), 7.1 (4H, t), 7.5 (4H, m), 7.9 (1H, s).

EXAMPLE 9 Preparation of bis(4-Fluorophenyl)methyl(5-mercapto-1H-1,2,4-triazol-1-ylmethyl)silane, disulfide

To a solution of 3.5 g (0.010 mol) of bis(4-fluorophenyl)methyl(5-mercapto-1H-1,2,4-triazol-1-ylmethyl)silane and 1.0 mL (0.012 mol) of pyridine in 20 mL of methylene chloride cooled to 5° C. was added a solution of 0.25 mL (0.005 mol) of bromine in 10 mL of methylene chloride over 5 minutes, causing the reaction temperature to rise to 12°. The solution was stirred at 25° for 30 minutes, diluted with ether, washed with 7% aqueous NaHCO₃ (foaming) and brine, and evaporated. Flash chromatography using 20% ether/methylene chloride gave 2.4 g of the title compound as a viscous oil: ir (neat) 3420 (br), 1590, 1500, 1390, 1235, 1165, 1110, 1012, 825, 680 cm⁻¹ ; nmr (CDCl₃) δ 0.7 (3H, s), 4.2 (2H, s), 7.1 (4H, t), 7.4 (4H, m), 7.8 (1H, s); mass spectrum: highest m/e 347.

EXAMPLE 10 Preparation of bis(4-Fluorophenyl)methyl[5-(1,2-dithiapentyl)-1H-1,2,4-triazol-1-ylmethyl]silane

To a solution of 1.4 g (0.004 mol) of bis(4-fluorophenyl)methyl(5-mercapto-1H-1,2,4-triazol-1-ylmethyl)silane in 10 mL of chloroform at 25° was added 1.1 g (0.005 mol) of propylthiophthalimide. The mixture was stirred two hours, filtered, and evaporated. The residue was flash chromatographed using 0-10% ether/methylene chloride to give 1.5 g of the title disulfide as a thick oil: ir (neat) 2950, 1585, 1495, 1230, 1160, 1104, 820 cm⁻¹ ; nmr (CDCl₃) δ 0.7 (3H, s), 1.0 (3H, t), 1.7 (2H, m), 2.8 (2H, t), 4.2 (2H, s), 7.1 (4H, m), 7.5 (4H, m), 7.8 (1H, s).

EXAMPLE 11 Preparation of bis(4-Fluorophenyl)methyl(5-methylsulfinyl-1H-1,2,4-triazol-1-ylmethyl)silane

To a solution of 1.8 g (0.005 mol) of bis(4-fluorophenyl)methyl(5-methylthio-1H-1,2,4-triazol-1-ylmethyl)silane in 15 mL of methylene chloride cooled to 0° C. was added 1.1 g (0.005 mol) of m-chloroperbenzoic acid (80%). The reaction temperature rose to 10°. The reaction mixture was stirred at 25° for 3 hours, then diluted with methylene chloride, washed with 7% aqueous NaHCO₃ and brine, dried over Na₂ SO₄ and evaporated to give 2.1 g of the title compound as an oil, pure except for traces of solvent and starting material: n^(D) 1.5717; ir (neat) 3020, 1590, 1500, 1232, 1164, 1110, 1070, 825 cm⁻¹ ; nmr (CDCl₃) δ 0.7 (3H, s), 2.8 (3H, s), 4.6 (2H, ABq), 7.1 (4H, m), 7.5 (4H, m), 7.9 (1H, s).

EXAMPLE 12 Preparation of bis(4-Fluorophenyl)methyl(5-methylsulfonyl-1H-1,2,4-triazol-1-ylmethyl)silane

To a solution of 2.7 g (0.0074 mol) of bis(4-fluorophenyl)methyl(5-methylthio-1H-1,2,4-triazol-1-ylmethyl)silane in 50 mL of methylene chloride cooled to 0° was added 3.2 g (0.015 mol) of m-chloroperbenzoic acid (80%). The reaction mixture was allowed to warm to 25° and after 2 hours, was diluted with methylene chloride, washed with 3 portions of 7% aqueous NaHCO₃ and brine, dried over MgSO₄ and evaporated. Flash chromatography (2% ether/methylene chloride) gave 2.6 g of the title compound as a colorless oil: n_(D) 1.5595; ir (neat) 3025, 1590, 1500, 1328 (br), 1232, 1164, 1145, 1108, 957, 825, 764 cm⁻¹ ; nmr (CDCl₃) δ 0.74 (3H, s), 3.1 (3H, s), 4.6 (2H, s), 7.1 (4H, t), 7.5 (4H, m), 7.8 (1H, s).

EXAMPLE 13 Preparation of bis(4-Fluorophenyl)methyl[5-(N-phenylcarbamothio)-1H-1,2,4-triazol-1-ylmethyl]silane

To a solution of 3.5 g (0.010 mol) of bis(4-fluorophenyl)methyl(5-mercapto-1H-1,2,4-triazol-1-ylmethyl)silane and a catalytic amount of 4-dimethylaminopyridine in 10 mL of methylene chloride at 25° was added 1.3 mL (0.012 mol) of phenyl isocyanate over 5 minutes, with ice bath cooling. The mixture was stirred 2 hours at 25°, then diluted with ether, washed with 7% aqueous NaHCO₃ and brine, dried over Na₂ SO₄ and evaporated. Flash chromatography (methylene chloride) gave 4.1 g of the title compound as ivory crystals: m.p. 126°-128°; ir (nujol) 3450 (br), 1742, 1588, 1405, 1235, 1106, 826 cm⁻¹ ; nmr (CDCl₃) δ 0.8 (3H, s), 4.2 (2H, s), 7.0-7.7 (13H, m), 8.5 (1H, s), 12.4 (1H, br s).

EXAMPLE 14 Preparation of bis(4-Fluorophenyl)methyl(5 -trichloromethylthio-1H-1,2,4-triazol-1-ylmethyl)silane

To a solution of 4.0 g (0.013 mol) of bis(4-fluorophenyl)methyl(1H-1,2,4-triazol-1-ylmethyl)silane and 2.0 mL (0.014 mol) of triethylamine in 50 mL of methylene chloride at 6° was added 1.4 mL (0.013 mol) of perchloromethylmercaptan over 2 minutes. The reaction temperature rose 6°. The dark solution was stirred at 25° for 2 hours, then diluted with methylene chloride, washed with water and brine, and evaporated to give 3.6 g of the title compound as an oil: ir (neat) 3100, 3020, 2960, 1590, 1500; nmr (CDCl₃) δ 0.7 (3H, s), 4.4 (2H, s), 7.1 (4H, t), 7.5 (4H, dd), 8.1 (1H, s); mass spectrum: m/e 464.

EXAMPLE 15 Preparation of bis(4-Fluorophenyl)methyl(5-bromo-1H-1,2,4-triazol-1-ylmethyl)silane

A mixture of 1.5 g (0.0050 mol) of bis(4-fluorophenyl)(methyl)(1H-1,2,4-triazol-1-ylmethyl)silane, 0.98 g (0.0055 mol) of N-bromosuccinimide and ˜1 mg of azobisisobutyltronitrile in 10 mL of CCl₄ was warmed to 60°, then illuminated with a high intensity lamp (Roxter Model 5900) for 20 minutes. The mixture was cooled, filtered, and evaporated, and the residue was flash chromatographed (10% ether/methylene chloride) to give 1.7 g of the title compound as an oil: ir (neat) 3030, 2960, 1590, 1498, 1479, 1339, 1265, 1231, 1162, 1108, 1033, 825, 789, 733 cm⁻¹. nmr (CDCl₃) δ0.7 (s, 9H), 4.2 (s, 2H, 7.1 (t, 4H), 7.5 (m, 4H), 7.8 (s, 1H).

The compounds of Formula I set forth in the following table can be prepared using the methods described hereinabove.

In the tables, Ph is phenyl, and substituted phenyl groups are abbreviated, e.g., 4-F-Ph is 4-fluorophenyl, 2,6-MeO₂ -Ph is 2,6-dimethoxyphenyl and 4-(4-F-Ph)-Ph is 4-(4-fluorophenyl)phenyl. The substituent "-SS-" for X denotes the disulfide dimer of the corresponding mercaptans; "-SeSe-" denotes the analogous diselenides.

                                      TABLE I                                      __________________________________________________________________________      ##STR30##                                                                     Cmpd.                                                                          No. R.sub.1     R.sub.2    R.sub.3  X                                          __________________________________________________________________________     1.  4-FPh       4-FPh      Me       vinyl              oil.sup.46                  4-FPh       4-FPh      Me       allyl                                          4-FPh       4-FPh      Me       2-propenyl                                     4-FPh       4-FPh      Me       1-butenyl                                      4-FPh       4-FPh      Me       ethynyl                                        4-FPh       4-FPh      Me       F                                          2.  4-FPh       4-FPh      Me       Cl                 n.sup.D 1.5595          3.  4-FPh       4-FPh      Me       Br                 oil.sup.1               4.  4-FPh       4-FPh      Me       I                  m.p.                                                                           102-104°.sup                                                            .2                          4-FPh       4-FPh      Me       NO.sub.2                                   5.  4-FPh       4-FPh      Me       NH.sub.2           m.p.                                                                           151-153°             4-FPh       4-FPh      Me       MeNH                                           4-FPh       4-FPh      Me        -n-BuNH                                       4-FPh       4-FPh      Me        .sub.-i-PrNH                                  4-FPh       4-FPh      Me       CH.sub.2CHCH.sub.2 NH                          4-FPh       4-FPh      Me       PhCH.sub.2 NH                                  4-FPh       4-FPh      Me       Me.sub.2 N                                 6.  4-FPh       4-FPh      Me       SH                 m.p.                                                                           97-99°           7.  4-FPh       4-FPh      Me       SS                 oil.sup.3               8.  4-FPh       4-FPh      Me       SMe                n.sup.D 1.5750          9.  4-FPh       4-FPh      Me       S(O)Me             n.sup.D 1.5717          10. 4-FPh       4-FPh      Me       SO.sub.2 Me        n.sup.D 1.5595              4-FPh       4-FPh      Me       SCF.sub.2 H                                    4-FPh       4-FPh      Me       S(O)CF.sub.2 H                                 4-FPh       4-FPh      Me       SO.sub.2 CF.sub.2 H                        11. 4-FPh       4-FPh      Me       SCCl.sub.3         oil.sup.19                  4-FPh       4-FPh      Me       S(O)CCl.sub.3                                  4-FPh       4-FPh      Me       SO.sub.2 CCl.sub.3                             4-FPh       4-FPh      Me       SEt                                            4-FPh       4-FPh      Me       S(O)Et                                         4-FPh       4-FPh      Me       SO.sub.2 Et                                    4-FPh       4-FPh      Me       SCF.sub.2 CF.sub.2 H                           4-FPh       4-FPh      Me       S(O)CF.sub.2 CF.sub.2 H                        4-FPh       4-FPh      Me       SO.sub.2 CF.sub.2 CF.sub.2 H                   4-FPh       4-FPh      Me       SCH.sub.2 CF.sub.3                             4-FPh       4-FPh      Me       S(O)CH.sub.2 CF.sub.3                          4-FPh       4-FPh      Me       SO.sub.2 CH.sub.2 CF.sub.3                     4-FPh       4-FPh      Me       SCH.sub.2 CH.sub.2 F                           4-FPh       4-FPh      Me       S(O)CH.sub.2 CH.sub.2 F                        4-FPh       4-FPh      Me       SO.sub.2 CH.sub.2 CH.sub.2 F                   4-FPh       4-FPh      Me       SCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                           Br                                         12. 4-FPh       4-FPh      Me       S -n-Pr            n.sup.D 1.5637          13. 4-FPh       4-FPh      Me       S(O) -n-Pr         n.sup.D 1.5477          14. 4-FPh       4-FPh      Me       SO.sub.2 -n-Pr     n.sup.D 1.5518              4-FPh       4-FPh      Me       SCH.sub.2 CHMe.sub.2                           4-FPh       4-FPh      Me       S(O)CH.sub.2 CHMe.sub.2                        4-FPh       4-FPh      Me       SO.sub.2 CH.sub.2 CHMe.sub.2               15. 4-FPh       4-FPh      Me       SCH.sub.2 CH.sub.2 CHMe.sub.2                                                                     n.sup.D 1.5528          16. 4-FPh       4-FPh      Me       S(O)CH.sub.2 CH.sub.2 CHMe.sub.2                                                                  n.sup.D 1.5467          17. 4-FPh       4-FPh      Me       SO.sub.2 CH.sub.2 CH.sub.2 CHMe.sub.2                                                             n.sup.D 1.5281          18. 4-FPh       4-FPh      Me       SCH.sub.2 CHCH.sub.2                                                                              oil.sup.4                   4-FPh       4-FPh      Me       S(O)CH.sub.2 CHCH.sub.2                    19. 4-FPh       4-FPh      Me       SO.sub.2 CH.sub.2 CHCH.sub.2                                                                      oil.sup.5               20. 4-FPh       4-FPh      Me       SCH.sub.2 SCN      oil.sup.6               21. 4-FPh       4-FPh      Me       S(O)CH.sub.2 SCN   m.p.                                                                           109-112°         22. 4-FPh       4-FPh      Me       SO.sub.2 CH.sub.2 SCN                                                                             m.p.                                                                           73-76°               4-FPh       4-FPh      Me       SCHCH.sub.2                                    4-FPh       4-FPh      Me       S(O)CHCH.sub.2                                 4-FPh       4-FPh      Me       SO.sub.2 CHCH.sub.2                            4-FPh       4-FPh      Me       SCHCHCH.sub.2 CH.sub.3                         4-FPh       4-FPh      Me       S(O)CHCHCH.sub.2 CH.sub.3                      4-FPh       4-FPh      Me       SO.sub.2 CHCHCH.sub.2 CH.sub.3                 4-FPh       4-FPh      Me       SCHCMe.sub.2                                   4-FPh       4-FPh      Me       S(O)CHCMe.sub.2                                4-FPh       4-FPh      Me       SO.sub.2 CHCMe.sub.2                       23. 4-FPh       4-FPh      Me       SCH(Me)CN          oil.sup.44              24. 4-FPh       4-FPh      Me       SCH.sub.2 CN       oil.sup.7               25. 4-F Ph      4-FPh      Me       S(O)CH.sub.2 CN    oil.sup.8               26. 4-FPh       4-FPh      Me       SO.sub.2 CH.sub.2 CN                                                                              oil.sup.9               27. 4-FPh       4-FPh      Me       SCH.sub.2 COMe     oil.sup.37              28. 4-FPh       4-FPh      Me       SO.sub.2 CH.sub.2 COMe                                                                            oil.sup.42              29. 4-FPh       4-FPh      Me       SCH.sub.2 COCH.sub.2 CO.sub.2                                                                     oil.sup.43              30. 4-FPh       4-FPh      Me       SCH.sub.2 CO.sub.2 H                                                                              oil.sup.36                  4-FPh       4-FPh      Me       S(O)CH.sub.2 CO.sub.2 H                        4-FPh       4-FPh      Me       SO.sub.2 CH.sub.2 CO.sub.2 H               31. 4-FPh       4-FPh      Me       SCH.sub.2 CO.sub.2 Me                                                                             oil.sup.10              32. 4-FPh       4-FPh      Me       S(O)CH.sub.2 CO.sub.2 Me                                                                          m.p.                                                                           86-89°           33. 4-FPh       4-FPh      Me       SO.sub.2 CH.sub.2 CO.sub.2 Me                                                                     semi-solid.sup.11           4-FPh       4-FPh      Me       SCH.sub.2 CO.sub.2 -n-Pr                       4-FPh       4-FPh      Me       S(O)CH.sub.2 CO.sub.2 -n-Pr                    4-FPh       4-FPh      Me       SO.sub.2 CH.sub.2 CO.sub.2 -n-Pr               4-FPh       4-FPh      Me       SCH.sub.2 CO.sub.2  .sub.-t-Bu                 4-FPh       4-FPh      Me       S(O)CH.sub.2 CO.sub.2 .sub.-t-Bu               4-FPh       4-FPh      Me       SO.sub.2 CH.sub.2 CO.sub.2 .sub.-t-Bu          4-FPh       4-FPh      Me       SCH.sub.2 CO.sub.2 CH.sub.2 CHCH.sub.2                                         5                                              4-FPh       4-FPh      Me       S(O)CH.sub.2 CO.sub.2 CH.sub.2 Ph              4-FPh       4-FPh      Me       SO.sub.2 CH.sub.2 CO.sub.2 Ph                  4-FPh       4-FPh      Me       S(O)CH.sub.2 CO.sub.23,5-Cl.sub.2Ph        34. 4-FPh       4-FPh      Me       SCH.sub.2 CCH      oil.sup.12                  4-FPh       4-FPh      Me       S(O)CH.sub.2 CCH                               4-FPh       4-FPh      Me       SO.sub.2 CH.sub.2 CCH                          4-FPh       4-FPh      Me       SCH.sub.2 CCMe                                 4-FPh       4-FPh      Me       SCCCH.sub.2 CH.sub.3                           4-FPh       4-FPh      Me       SO.sub.2 CH.sub.2 CH.sub.3 CCH                 4-FPh       4-FPh      Me       SCH.sub.2 NO.sub.2                             4-FPh       4-FPh      Me       S(O)CH.sub.2 NO.sub.2                          4-FPh       4-FPh      Me       SO.sub.2 CH.sub.2 NO.sub.2                 35. 4-FPh       4-FPh      Me       SCH.sub.2 Ph       oil.sup.13              36. 4-FPh       4-FPh      Me       S(O)CH.sub.2 Ph    oil.sup.30              37. 4-FPh       4-FPh      Me       SO.sub.2 CH.sub.2 Ph                                                                              oil.sup.31              38. 4-FPh       4-FPh      Me       SCH.sub.2 OCH.sub.3                                                                               oil.sup.14                  4-FPh       4-FPh      Me       S(O)CH.sub.2 OCH.sub.3                         4-FPh       4-FPh      Me       SO.sub.2 CH.sub.2 OCH.sub.3                39. 4-FPh       4-FPh      Me       SSMe               oil.sup.15                  4-FPh       4-FPh      Me       SSEt                                       40. 4-FPh       4-FPh      Me       SS -n-Pr           oil.sup.16              41. 4-FPh       4-FPh      Me       SS .sub.-i-Pr      oil.sup.17                  4-FPh       4-FPh      Me       SS -n-Bu                                   42. 4-FPh       4-FPh      Me       SSCH.sub.2 Ph      oil.sup.32              43. 4-FPh       4-FPh      Me       SSCCl.sub.3        m.p.                                                                           98°(d)           44. 4-FPh       4-FPh      Me       SSPh               oil.sup.18                  4-FPh       4-FPh      Me       SS4-FPh                                        4-FPh       4-FPh      Me       SS3-CF.sub.3Ph                                 4-FPh       4-FPh      Me       SS4-MeOPh                                      4-FPh       4-FPh      Me       SNH.sub.2                                      4-FPh       4-FPh      Me       SNHMe                                          4-FPh       4-FPh      Me       SNHCH.sub.2 CHCH.sub.2                         4-FPh       4-FPh      Me       SNHPh                                          4-FPh       4-FPh      Me       SNMe.sub.2                                     4-FPh       4-FPh      Me       SN( .sub.-i-Bu)Ph                              4-FPh       4-FPh      Me       SN(CH.sub.2 Ph)Me                              4-FPh       4-FPh      Me       SNEt.sub.2                                     4-FPh       4-FPh      Me       SNH2-MePh                                      4-FPh       4-FPh      Me       SeH                                            4-FPh       4-FPh      Me       SeSe                                           4-FPh       4-FPh      Me       SeMe                                           4-FPh       4-FPh      Me       Se(O)Me                                        4-FPh       4-FPh      Me       SePh                                           4-FPh       4-FPh      Me       Se(O)Ph                                        4-FPh       4-FPh      Me       SCN                                            4-FPh       4-FPh      Me       NHNH.sub.2                                     4-FPh       4-FPh      Me       NMeNMe.sub.2                                   4-FPh       4-FPh      Me       NHNHPh                                         4-FPh       4-FPh      Me       NMeNHMe                                    45. 4-FPh       4-FPh      Me       NHCOCF.sub.3       m.p.                                                                           139-142°         46. 4-FPh       4-FPh      Me       NH.sub.3.sup.+ Cl.sup.-                                                                           m.p.                                                                           240-245°             4-FPh       4-FPh      Me                                                                                       ##STR31##                                 47. 4-FPh       4-FPh      Me                                                                                       ##STR32##         oil.sup.20                  4-FPh       4-FPh      Me                                                                                       ##STR33##                                     4-FPh       4-FPh      Me                                                                                       ##STR34##                                 48. 4-FPh       4-FPh      Me                                                                                       ##STR35##         oil.sup.21              49. 4-FPh       4-FPh      Me                                                                                       ##STR36##         oil.sup.34                  4-FPh       4-FPh      Me                                                                                       ##STR37##                                     4-FPh       4-FPh      Me                                                                                       ##STR38##                                     4-FPh       4-FPh      Me                                                                                       ##STR39##                                 50. 4-FPh       4-FPh      Me                                                                                       ##STR40##         oil.sup.33              51. 4-FPh       4-FPh      Me                                                                                       ##STR41##         m.p.                                                                           126-128°         52. 4-FPh       4-FPh      Me                                                                                       ##STR42##         m.p.                                                                           121-124°         53. 4-FPh       4-FPh      Me                                                                                       ##STR43##         m.p.                                                                           94-97°           54. 4-FPh       4-FPh      Me                                                                                       ##STR44##         m.p.                                                                           121-124°             4-FPh       4-FPh      Me                                                                                       ##STR45##                                     4-FPh       4-FPh      Me                                                                                       ##STR46##                                     4-FPh       4-FPh      Me                                                                                       ##STR47##                                     4-FPh       4-FPh      Me                                                                                       ##STR48##                                     4-FPh       4-FPh      Me                                                                                       ##STR49##                                     4-FPh       4-FPh      Me                                                                                       ##STR50##                                     4-FPh       4-FPh      Me                                                                                       ##STR51##                                     4-FPh       4-FPh      Me                                                                                       ##STR52##                                     4-FPh       4-FPh      Me                                                                                       ##STR53##                                     4-FPh       4-FPh      Me                                                                                       ##STR54##                                     4-FPh       4-FPh      Me                                                                                       ##STR55##                                     4-FPh       4-FPh      Me                                                                                       ##STR56##                                     4-FPh       4-FPh      Me                                                                                       ##STR57##                                     4-FPh       4-FPh      Me                                                                                       ##STR58##                                     4-FPh       4-FPh      Me                                                                                       ##STR59##                                     4-FPh       4-FPh      Me                                                                                       ##STR60##                                     4-FPh       4-FPh      Me                                                                                       ##STR61##                                     4-FPh       4-FPh      Me       MeNC(OMe)S                                     4-FPh       4-FPh      Me       PhNC(OMe)S                                     4-FPh       4-FPh      Me        -n-BuNC(OEt)S                             55. 4-FPh       4-FPh      Me       CH.sub.2 OH        m.p.                                                                           112-116°         56. 4-FPh       4-FPh      Me       CH(OH)Me           oil.sup.22                  4-FPh       4-FPh      Me       CH(OH)Et                                   57. 4-FPh       4-FPh      Me       CH(OH) .sub.-i-Pr  m.p.                                                                           110-113°         58. 4-FPh       4-FPh      Me       CH(OH)Ph           semi-solid.sup.23       59. 4-FPh       4-FPh      Me       CH(OH)vinyl        m.p.                                                                           78-80°           60. 4-FPh       4-FPh      Me       CH(OH)CHCHCH.sub.3 m.p.                                                                           95-101°          61. 4-FPh       4-FPh      Me       CH(OH)CHCHPh       glass.sup.24                4-FPh       4-FPh      Me       CH(OH)2-propenyl                           62. 4-FPh       4-FPh      Me       CH(OH)C(CH.sub.3)CHPh                                                                             oil.sup.25              63. 4-FPh       4-FPh      Me       CH(OH)2,5-MeO.sub.2Ph                                                                             m.p.                                                                           120-121°         64. 4-FPh       4-FPh      Me       CH(OH)2,5-Me.sub.2Ph                                                                              m.p.                                                                           140-142°             4-FPh       4-FPh      Me       CH(OH)4-ClPh                                   4-FPh       4-FPh      Me       CH(OH)CH.sub.2 Ph                          65. 4-FPh       4-FPh      Me                                                                                       ##STR62##         m.p.                                                                           60-62°           66. 4-FPh       4-FPh      Me       CH(OH)C(CH.sub.2)CHMe.sub.2                                                                       m.p.                                                                           82-85°           67. 4-FPh       4-FPh      Me       CHO                n.sub.D 1.5612          68. 4-FPh       4-FPh      Me       COMe               oil.sup.26                  4-FPh       4-FPh      Me       COEt                                           4-FPh       4-FPh      Me       CO .sub.-i-Pr                                  4-FPh       4-FPh      Me       COCHCH.sub.2                                   4-FPh       4-FPh      Me       COCHCHCH.sub.3                                 4-FPh       4-FPh      Me       COCHCHPh                                   69. 4-FPh       4-FPh      Me       COC(CH.sub.3)CHPh  oil.sup.38                  4-FPh       4-FPh      Me       COC(CH.sub.3)CH.sub.2                      70. 4-FPh       4-FPh      Me       COPh               oil.sup.35              71. 4-FPh       4-FPh      Me       CO2,5-MeO.sub.2Ph  oil.sup.39              72. 4-FPh       4-FPh      Me       CO2,5-Me.sub.2Ph   oil.sup.27                  4-FPh       4-FPh      Me       CO4-ClPh                                       4-FPh       4-FPh      Me       COCH.sub.2 Ph                              73. 4-FPh       4-FPh      Me       COC(CH.sub.2)CHMe.sub.2                                                                           oil.sup.45              74. 4-FPh       4-FPh      Me                                                                                       ##STR63##         oil.sup.40              75. 4-FPh       4-FPh      Me       COC(Me)CHCH(Me)CH.sub.2 CHCH.sub.2                                                                oil.sup.41                  4-FPh       4-FPh      Me       PO(OH).sub.2                                   4-FPh       4-FPh      Me       PO(OMe).sub.2                              76. 4-FPh       4-FPh      Me       PO(OEt).sub.2      oil.sup.28                  4-FPh       4-FPh      Me       PO(OCH.sub.2 Ph).sub.2                         4-FPh       4-FPh      Me       PO(O .sub.-i-Pr).sub.2                         4-FPh       4-FPh      Me       CONH.sub.2                                     4-FPh       4-FPh      Me       CONHMe                                         4-FPh       4-FPh      Me       CONMe.sub.2                                    4-FPh       4-FPh      Me       CONHCH.sub.2 CHCH.sub.2                        4-FPh       4-FPh      Me       CONH -n-Bu                                     4-FPh       4-FPh      Me       CONH .sub.-i-Pr                                4-FPh       4-FPh      Me       CSNH.sub.2                                     4-FPh       4-FPh      Me       CSNMe.sub.2                                    4-FPh       4-FPh      Me       CSNHMe                                         4-FPh       4-FPh      Me       CSNH .sub.-i-Pr                                4-FPh       4-FPh      Me       CSNHCH.sub.2 CHCH.sub.2                        4-FPh       4-FPh      Me       CSNH -n-Bu                                     4-FPh       4-FPh      Me       CSNHCH.sub.2 Ph                            77. 4-FPh       4-FPh      Me       CO.sub.2 H         m.p.                                                                           84-100°              4-FPh       4-FPh      Me       CO.sub.2 Li                                78. 4-FPh       4-FPh      Me       CO.sub.2 Me        oil.sup.29                  4-FPh       4-FPh      Me       CO.sub.2 Et                                    4-FPh       4-FPh      Me       CO.sub.2 CH.sub.2 CHCH.sub.2                   4-FPh       4-FPh      Me       CO.sub.2 .sub.-t-Bu                            4-FPh       4-FPh      Me       CO.sub.2 CH.sub. 2 Ph                          4-FPh       4-FPh      Me       CO.sub.2 Ph                                    4-FPh       4-FPh      Me       CO.sub.24-MePh                                 4-FPh       4-FPh      Me       CS.sub.2 H                                 79. 4-FPh       4-FPh      Me       CS.sub.2 Me        m.p. 57-60°                                                             C.                          4-FPh       4-FPh      Me       CS.sub.2 Et                                80. 4-FPh       4-FPh      Me       CS.sub.2 CH.sub.2 CHCH.sub.2                                                                      n.sub.D 1.6001              4-FPh       4-FPh      Me       CS.sub.2 CH.sub.2 Ph                       81. 4-FPh       4-FPh      Me       COSMe              n.sub.D 1.5694          82. 4-FPh       4-FPh      Me       COSEt              n.sub.D 1.5658              4-FPh       4-FPh      Me       COSCH.sub.2 Ph                             83. 4-FPh       4-FPh      Me       COSCH.sub.2 CHCH.sub.2                                                                            n.sub.D 1.5690              4-FPh       4-FPh      Me       COS .sub.-i-Pr                             84. 4-FPh       Ph         Me       SH                 m.p.                                                                           114-115°         85. Ph          Ph         Me       SH                 m.p.                                                                           157-158°         86. 4-ClPh      4-ClPh     Me       SH                 m.p.                                                                           157-158°         87. 4-ClPh      Ph         Me       SH                 m.p.                                                                           138-141°             4-FPh       2-FPh      Me       SH                                             4-FPh       2,4-F.sub.2Ph                                                                             Me       SH                                             4-FPh       4-FPh      vinyl    SH                                             4-FPh       4-FPh      allyl    SH                                         88. 4-PhPh      Me         Me       SH                 m.p.                                                                           153-157°             4-PhPh      vinyl      vinyl    SH                                             4-FPh       4-FPh      OH       SH                                             4-FPh       4-FPh      O .sub.-t-Bu                                                                            SH                                             4-FPh       4-FPh      Et       SH                                             2,4-Cl.sub.2Ph                                                                             Me         Me       SH                                              ##STR64##  4-FPh      Me       SH                                             4-FPh       Ph         Me       SS                                             Ph          Ph         Me       SS                                             4-ClPh      4-ClPh     Me       SS                                             4-ClPh      Ph         Me       SS                                             4-FPh       2-FPh      Me       SS                                             4-FPh       2,4-F.sub.2Ph                                                                             Me       SS                                             4-FPh       4-FPh      vinyl    SS                                             4-FPh       4-FPh      allyl    SS                                             4-PhPh      Me         Me       SS                                             4-PhPh      vinyl      vinyl    SS                                             4-FPh       4-FPh      OH       SS                                             4-FPh       4-FPh      O .sub.-t-Bu                                                                            SS                                             4-FPh       4-FPh      Et       SS                                             2,4-Cl.sub.2Ph                                                                             Me         Me       SS                                              ##STR65##  4-FPh      Me       SS                                             4-FPh       Ph         Me       SMe                                            Ph          Ph         Me       SMe                                            4-ClPh      4-ClPh     Me       SMe                                            4-ClPh      Ph         Me       SMe                                            4-FPh       2-FPh      Me       SMe                                            4-FPh       2,4-F.sub.2Ph                                                                             Me       SMe                                            4-FPh       4-FPh      vinyl    SMe                                            4-FPh       4-FPh      allyl    SMe                                            4-PhPh      Me         Me       SMe                                            4-PhPh      vinyl      vinyl    SMe                                            4-FPh       4-FPh      OH       SMe                                            4-FPh       4-FPh      O .sub.-t-Bu                                                                            SMe                                            4-FPh       4-FPh      Et       SMe                                            2,4-Cl.sub.2Ph                                                                             Me         Me       SMe                                             ##STR66##  4-FPh      Me       SMe                                            4-FPh       Ph         Me       S(O)Me                                         Ph          Ph         Me       S(O)Me                                         4-ClPh      4-ClPh     Me       S(O)Me                                         4-ClPh      Ph         Me       S(O)Me                                         4-FPh       2-FPh      Me       S(O)Me                                         4-FPh       2,4-F.sub.2Ph                                                                             Me       S(O)Me                                         4-FPh       4-FPh      vinyl    S(O)Me                                         4-FPh       4-FPh      allyl    S(O)Me                                         4-PhPh      Me         Me       S(O)Me                                         4-PhPh      vinyl      vinyl    S(O)Me                                         4-FPh       4-FPh      OH       S(O)Me                                         4-FPh       4-FPh      O .sub.-t-Bu                                                                            S(O)Me                                         4-FPh       4-FPh      Et       S(O)Me                                         2,4-Cl.sub.2Ph                                                                             Me         Me       S(O)Me                                          ##STR67##  4-FPh      Me       S(O)Me                                         4-FPh       Ph         Me       SO.sub.2 Me                                    Ph          Ph         Me       SO.sub.2 Me                                    4-ClPh      4-ClPh     Me       SO.sub.2 Me                                    4-ClPh      Ph         Me       SO.sub.2 Me                                    4-FPh       2-FPh      Me       SO.sub.2 Me                                    4-FPh       2,4-F.sub.2Ph                                                                             Me       SO.sub.2 Me                                    4-FPh       4-FPh      vinyl    SO.sub.2 Me                                    4-FPh       4-FPh      allyl    SO.sub.2 Me                                    4-PhPh      Me         Me       SO.sub.2 Me                                    4-PhPh      vinyl      vinyl    SO.sub.2 Me                                    4-FPh       4-FPh      OH       SO.sub.2 Me                                    4-FPh       4-FPh      O .sub.-t-Bu                                                                            SO.sub.2 Me                                    4-FPh       4-FPh      Et       SO.sub.2 Me                                    2,4-Cl.sub.2Ph                                                                             Me         Me       SO.sub.2 Me                                     ##STR68##  4-FPh      Me       SO.sub.2 Me                                    4-FPh       Ph         Me       SSMe                                           Ph          Ph         Me       SSMe                                           4-ClPh      4-ClPh     Me       SSMe                                           4-ClPh      Ph         Me       SSMe                                           4-FPh       2-FPh      Me       SSMe                                           4-FPh       2,4-F.sub.2Ph                                                                             Me       SSMe                                           4-FPh       4-FPh      vinyl    SSMe                                           4-FPh       4-FPh      allyl    SSMe                                           4-PhPh      Me         Me       SSMe                                           4-PhPh      vinyl      vinyl    SSMe                                           4-FPh       4-FPh      OH       SSMe                                           4-FPh       4-FPh      O .sub.-t-Bu                                                                            SSMe                                           4-FPh       4-FPh      Et       SSMe                                           2,4-Cl.sub.2Ph                                                                             Me         Me       SSMe                                            ##STR69##  4-FPh      Me       SSMe                                           4-FPh       Ph         Me                                                                                       ##STR70##                                     Ph          Ph         Me                                                                                       ##STR71##                                     4-ClPh      4-ClPh     Me                                                                                       ##STR72##                                     4-ClPh      Ph         Me                                                                                       ##STR73##                                     4-FPh       2-FPh      Me                                                                                       ##STR74##                                     4-FPh       2,4-F.sub.2Ph                                                                             Me                                                                                       ##STR75##                                     4-FPh       4-FPh      vinyl                                                                                    ##STR76##                                     4-FPh       4-FPh      allyl                                                                                    ##STR77##                                     4-PhPh      Me         Me                                                                                       ##STR78##                                     4-PhPh      vinyl      vinyl                                                                                    ##STR79##                                     4-FPh       4-FPh      OH                                                                                       ##STR80##                                     4-FPh       4-FPh      O .sub.-t-Bu                                                                             ##STR81##                                     4-FPh       4-FPh      Et                                                                                       ##STR82##                                     2,4-Cl.sub.2Ph                                                                             Me         Me                                                                                       ##STR83##                                      ##STR84##  4-FPh      Me                                                                                       ##STR85##                                     4-FPh       Ph         Me                                                                                       ##STR86##                                     Ph          Ph         Me                                                                                       ##STR87##                                     4-ClPh      4-ClPh     Me                                                                                       ##STR88##                                     4-ClPh      Ph         Me                                                                                       ##STR89##                                     4-FPh       2-FPh      Me                                                                                       ##STR90##                                     4-FPh       2,4-F.sub.2Ph                                                                             Me                                                                                       ##STR91##                                     4-FPh       4-FPh      vinyl                                                                                    ##STR92##                                     4-FPh       4-FPh      allyl                                                                                    ##STR93##                                     4-PhPh      Me         Me                                                                                       ##STR94##                                     4-PhPh      vinyl      vinyl                                                                                    ##STR95##                                     4-FPh       4-FPh      OH                                                                                       ##STR96##                                     4-FPh       4-FPh      O .sub.-t-Bu                                                                             ##STR97##                                     4-FPh       4-FPh      Et                                                                                       ##STR98##                                     2,4-Cl.sub.2Ph                                                                             Me         Me                                                                                       ##STR99##                                      ##STR100## 4-FPh      Me                                                                                       ##STR101##                                    4-FPh       Ph         Me                                                                                       ##STR102##                                    Ph          Ph         Me                                                                                       ##STR103##                                    4-ClPh      4-ClPh     Me                                                                                       ##STR104##                                    4-ClPh      Ph         Me                                                                                       ##STR105##                                    4-FPh       2-FPh      Me                                                                                       ##STR106##                                    4-FPh       2,4-F.sub.2Ph                                                                             Me                                                                                       ##STR107##                                    4-FPh       4-FPh      vinyl                                                                                    ##STR108##                                    4-FPh       4-FPh      allyl                                                                                    ##STR109##                                    4-PhPh      Me         Me                                                                                       ##STR110##                                    4-PhPh      vinyl      vinyl                                                                                    ##STR111##                                    4-FPh       4-FPh      OH                                                                                       ##STR112##                                    4-FPh       4-FPh      O .sub.-t-Bu                                                                             ##STR113##                                    4-FPh       4-FPh      Et                                                                                       ##STR114##                                    2,4-Cl.sub.2Ph                                                                             Me         Me                                                                                       ##STR115##                                     ##STR116## 4-FPh      Me                                                                                       ##STR117##                                    4-FPh       Ph         Me       F                                              Ph          Ph         Me       F                                              4-ClPh      4-ClPh     Me       F                                              4-ClPh      Ph         Me       F                                              4-FPh       2-FPh      Me       F                                              4-FPh       2,4-F.sub.2Ph                                                                             Me       F                                              4-FPh       4-FPh      vinyl    F                                              4-FPh       4-FPh      allyl    F                                              4-PhPh      Me         Me       F                                              4-PhPh      vinyl      vinyl    F                                              4-FPh       4-FPh      OH       F                                              4-FPh       4-FPh      O .sub.-t-Bu                                                                            F                                              4-FPh       4-FPh      Et       F                                              2,4-Cl.sub.2Ph                                                                             Me         Me       F                                               ##STR118## 4-FPh      Me       F                                              4-FPh       Ph         Me       Cl                                             Ph          Ph         Me       Cl                                             4-ClPh      4-ClPh     Me       Cl                                             4-ClPh      Ph         Me       Cl                                             4-FPh       2-FPh      Me       Cl                                             4-FPh       2,4-F.sub.2Ph                                                                             Me       Cl                                             4-FPh       4-FPh      vinyl    Cl                                             4-FPh       4-FPh      allyl    Cl                                             4-PhPh      Me         Me       Cl                                             4-Ph Ph     vinyl      vinyl    Cl                                             4-FPh       4-FPh      OH       Cl                                             4-FPh       4-FPh      O .sub.-t-Bu                                                                            Cl                                             4-FPh       4-FPh      Et       Cl                                             2,4-Cl.sub.2Ph                                                                             Me         Me       Cl                                              ##STR119## 4-FPh      Me       Cl                                             4-FPh       Ph         Me       CHO                                            Ph          Ph         Me       CHO                                            4-ClPh      4-ClPh     Me       CHO                                            4-ClPh      Ph         Me       CHO                                            4-FPh       2-FPh      Me       CHO                                            4-FPh       2,4-F.sub.2Ph                                                                             Me       CHO                                            4-FPh       4-FPh      vinyl    CHO                                            4-FPh       4-FPh      allyl    CHO                                            4-PhPh      Me         Me       CHO                                            4-PhPh      vinyl      vinyl    CHO                                            4-FPh       4-FPh      OH       CHO                                            4-FPh       4-FPh      O .sub.-t-Bu                                                                            CHO                                            4-FPh       4-FPh      Et       CHO                                            2,4-Cl.sub.2Ph                                                                             Me         Me       CHO                                             ##STR120## 4-FPh      Me       CHO                                            4-FPh       Ph         Me       I                                              Ph          Ph         Me       I                                              4-ClPh      4-ClPh     Me       I                                              4-ClPh      Ph         Me       I                                              4-FPh       2-FPh      Me       I                                              4-FPh       2,4-F.sub.2Ph                                                                             Me       I                                              4-FPh       4-FPh      vinyl    I                                              4-FPh       4-FPh      allyl    I                                              4-PhPh      Me         Me       I                                              4-PhPh      vinyl      vinyl    I                                              4-FPh       4-FPh      OH       I                                              4-FPh       4-FPh      O .sub.-t-Bu                                                                            I                                              4-FPh       4-FPh      Et       I                                              2,4-Cl.sub.2Ph                                                                             Me         Me       I                                               ##STR121## 4-FPh      Me       I                                              PhCHCH      CH.sub.3   CH.sub.3 SH                                             4-FPhCHCH   4-FPh      CH.sub.3 SH                                             (CH.sub.3).sub.2 CCH.sub.2                                                                 2,4-F.sub.2Ph                                                                             CH.sub.3 SH                                             CH.sub.2C(Et)                                                                              4-ClPh     CH.sub.3 SH                                             1-napthyl   2-CF.sub.3Ph                                                                              CH.sub.3 SH                                             2-napthyl   CH.sub.3   CH.sub.3 SH                                             PhCC        4-FPh      4-FPh    SH                                              -n-BuCC    4-FPh      CH.sub.3 SH                                             CH.sub.3 C C                                                                               4-FPh      4-FPh    SH                                             4-PhPh      CH.sub.2 CHC(CH.sub.3).sub.2                                                              O .sub.-t-Bu                                                                            SH                                             4-FPh       3-CF.sub.3Ph                                                                              Me       SH                                             4-MeOPh     4-ClPh      -n-Bu   SH                                             4-(4-FPh)Ph vinyl      O .sub.-t-Bu                                                                            SH                                             4-CHF.sub.2 OPh                                                                            Ph         Me       SH                                             4-BrPh       -n-hexyl  Me       SH                                             4-MePh      4-MePh     Me       SH                                             4-CF.sub.3 OPh                                                                             4-CF.sub.3 OPh                                                                            Me       SH                                             4-( -n-Bu)Ph                                                                               4-FPh      Me       SH                                             2,4-Cl.sub.2Ph                                                                             CH.sub.2 C(Me)CH.sub.2                                                                    CH.sub.2 C(Me)CH.sub.2                                                                  SH                                             4-FPh       4-FPh      O -n-Bu  SH                                              .sub.-t-BuCC                                                                              4-FPh      Me       SH                                             2,6-MeO.sub.2Ph                                                                            Me         Me       SH                                             4-( .sub.-t-Bu)Ph                                                                          Me         Me       SH                                              ##STR122## 4-FPh      Me       SH                                             PhCHCH      CH.sub.3   CH.sub.3 SS                                             4-FPhCHCH   4-FPh      CH.sub.3 SS                                             (CH.sub.3).sub.2 CCH.sub.2                                                                 2,4-F.sub.2Ph                                                                             CH.sub.3 SS                                             CH.sub.2C(Et)                                                                              4-ClPh     CH.sub.3 SS                                             1-napthyl   2-CF.sub.3Ph                                                                              CH.sub.3 SS                                             2-napthyl   CH.sub.3   CH.sub.3 SS                                             PhCC        4-FPh      4-FPh    SS                                              -n-BuCC    4-FPh      CH.sub.3 SS                                             CH.sub.3 CC 4-FPh      4-FPh    SS                                             4-PhPh      CH.sub.2 CHC(CH.sub.3).sub.2                                                              O .sub.-t-Bu                                                                            SS                                             4-FPh       3-CF.sub.3Ph                                                                              Me       SS                                             4-MeOPh     4-ClPh      -n-Bu   SS                                             4-(4-FPh)Ph vinyl      O .sub.-t-Bu                                                                            SS                                             4-CHF.sub.2 OPh                                                                            Ph         Me       SS                                             4-BrPh        -n-hexyl Me       SS                                             4-MePh      4-MePh     Me       SS                                             4-CF.sub.3 OPh                                                                             4-CF.sub.3 OPh                                                                            Me       SS                                             4-( -n-Bu)Ph                                                                               4-FPh      Me       SS                                             2,4-Cl.sub.2Ph                                                                             CH.sub.2 C(Me)CH.sub.2                                                                    CH.sub.2 C(Me)CH.sub.2                                                                  SS                                             4-FPh       4-FPh      O -n-Bu  SS                                              .sub.-t-BuCC                                                                              4-FPh      Me       SS                                             2,6-MeO.sub.2Ph                                                                            Me         Me       SS                                             4-( .sub.-t-Bu)Ph                                                                          Me         Me       SS                                              ##STR123## 4-FPh      Me       SS                                             PhCHCH      CH.sub.3   CH.sub.3                                                                                 ##STR124##                                    4-FPhCHCH   4-FPh      CH.sub.3                                                                                 ##STR125##                                    (CH.sub.3).sub.2 CCH.sub.2                                                                 2,4-F.sub.2Ph                                                                             CH.sub.3                                                                                 ##STR126##                                    CH.sub.2C(Et)                                                                              4-ClPh     CH.sub.3                                                                                 ##STR127##                                    1-napthyl   2-CF.sub.3Ph                                                                              CH.sub.3                                                                                 ##STR128##                                    2-napthyl   CH.sub.3   CH.sub.3                                                                                 ##STR129##                                    PhCC        4-FPh      4-FPh                                                                                    ##STR130##                                    BuCC        4-FPh      CH.sub.3                                                                                 ##STR131##                                    CH.sub.3 CC 4-FPh      4-FPh                                                                                    ##STR132##                                    4-PhPh      CH.sub.2 CHC(CH.sub.3).sub.2                                                              O .sub.-t-Bu                                                                             ##STR133##                                    4-FPh       3-CF.sub.3Ph                                                                              Me                                                                                       ##STR134##                                    4-MeOPh     4-ClPh      -n-Bu                                                                                   ##STR135##                                    4-(4-FPh)Ph vinyl      O .sub.-t-Bu                                                                             ##STR136##                                    4-CHF.sub.2 OPh                                                                            Ph         Me                                                                                       ##STR137##                                    4-BrPh       -n-hexyl  Me                                                                                       ##STR138##                                    4-MePh      4-MePh     Me                                                                                       ##STR139##                                    4-CF.sub.3 OPh                                                                             4-CF.sub.3 OPh                                                                            Me                                                                                       ##STR140##                                    4-( -n-Bu)Ph                                                                               4-FPh      Me                                                                                       ##STR141##                                    2,4-Cl.sub.2Ph                                                                             CH.sub.2 C(Me)CH.sub.2                                                                    CH.sub.2 C(Me)CH.sub.2                                                                   ##STR142##                                    4-FPh       4-FPh      O -n-Bu                                                                                  ##STR143##                                    t-BuC C     4-FPh      Me                                                                                       ##STR144##                                    2,6-MeO.sub.2Ph                                                                            Me         Me                                                                                       ##STR145##                                    4-( .sub.-t-Bu)Ph                                                                          Me         Me                                                                                       ##STR146##                                     ##STR147## 4-FPh      Me                                                                                       ##STR148##                                __________________________________________________________________________     Footnotes to Table I                                                           NMR Data (CDCl.sub.3); peak position in parts per million downfield from       tetramethylsilane.                                                             1. 0.7 (s), 4.2 (s), 7.2 (t), 7.6 (m), 7.8 (s).                                2. 0.7 (s), 4.2 (s), 7.1 (m), 7.5 (m), 7.8 (s).                                3. 0.7 (s), 4.2 (s), 7.1 (t), 7.4 (m), 7.8 (s).                                4. 0.7 (s), 3.7 (d), 4.0 (s), 5.1 (d), 5.2 (d), 5.8 (m), 7.1 (t), 7.5          (m), 7.8 (s).                                                                  5. 0.7 (s), 4.0 (d), 4.6 (s), 5.3 (m), 5.4 (d), 5.8 (m), 7.1 (t), 7.5          (m), 7.9 (s).                                                                  6. 0.7 (s), 4.0 (s), 4.6 (s), 7.1 (t), 7.5 (m), 7.9 (s).                       7. 0.8 (s), 3.9 (s), 4.0 (s), 7.1 (m), 7.5 (m), 7.8 (s).                       8. 0.8 (s), 4.1 (ABq), 4.6 (ABq), 7.1 (m), 7.5 (m), 8.0 (s).                   9. 0.8 (s), 4.4 (s), 4.6 (s), 7.1 (t), 7.5 (m), 8.0 (s).                       10. 0.7 (s), 3.7 (s), 3.9 (s), 4.0 (s), 7.1 (t), 7.7 (m), 7.8 (s).             11. 0.7 (s), 3.7 (s), 4.4 (s), 4.6 (s), 7.1 (t), 7.5 (m), 7.9 (s).             12. 0.7 (s), 2.2 (t), 3.8 (d), 4.1 (s), 7.1 (t), 7.5 (m), 7.8 (s).             13. 0.7 (s), 3.9 (s), 4.3 (s), 7.0 (t), 7.3 (s), 7.4 (m), 7.8 (s).             14. 0.8 (s), 3.3 (s), 4.3 (s), 5.3 (s), 7.1 (t), 7.6 (m), 7.8 (s).             15. 0.7 (s), 2.5 (s), 4.2 (s), 7.1 (t), 7.5 (m), 7.8 (s).                      16. 0.7 (s), 1.0 (t), 1.7 (m), 2.8 (t), 4.2 (s), 7.1 (m), 7.5 (m), 7.8         (s).                                                                           17. 0.7 (s), 1.3 (d), 3.2 (heptet), 4.2 (s), 7.1 (t), 7.5 (m), 7.8 (s).        18. 0.7 (s), 4.1 (s), 7.1 (t), 7.2-7.6 (m), 7.9 (s).                           19. 0.7 (s), 4.4 (s), 7.1 (t), 7.5 (d), 8.1 (s).                               20. 0.7 (s), 3.0 (d), 4.2 (s), 7.1 (t), 7.5 (m), 8.4 (s), 10.0 (br s).         21. 0.7 (s), 1.0 (t), 1.4 (m), 1.6 (m), 3.4 (approximate q), 4.2 (s), 7.1      (t), 7.6 (m), 8.4 (s).                                                         22. 0.7 (s), 1.4 (d), 2.9 (br d), 4.2 (s), 4.8 (m), 7.1 (m), 7.4 (m), 7.7      (s).                                                                           23. 0.6 (s), 3.6 (d), 3.9 (ABq), 5.8 (d), 6.9-7.1 (m), 7.2-7.4 (m), 7.8        (s).                                                                           24. 0.7 (s), 3.5 (br s), 4.2 (s), 5.4 (d), 6.2 (dd), 6.6 (d), 7.0 (m),         7.3 (s), 7.4 (m), 7.8 (s).                                                     25. 0.7 (s), 1.6 (s), 3.9 (br s), 4.1 (ABq), 5.2 (s), 6.6 (s), 7.0 (q),        7.2-7.5 (m), 7.8 (s).                                                          26. 0.7 (s), 2.5 (s), 4.8 (s), 7.0 (t), 7.4 (t), 7.8 (s).                      27. 0.8 (s), 2.3 (s), 4.9 (s), 7.0-7.3 (m), 7.5 (t), 7.9 (s).                  28. 0.7 (s), 1.3 (t), 4.0 (m), 4.7 (s), 7.0 (t), 7.5 (m), 7.9 (s).             29. 0.7 (s), 3.9 (s), 4.8 (s), 7.2 (t), 7.6 (m), 8.0 (s).                      30. 0.6 (s), 3.7, 4.2 (two d, ABq), 4.2, 4.4 (two d, ABq), 7.0 (m), 7.5        (m), 7.9 (s).                                                                  31. 0.6 (s), 4.1 (s), 4.5 (s), 7.0-7.7 (m), 7.9 (s).                           32. 0.7 (s), 4.1 (s), 4.2 (s), 7.1 (t), 7.5 (s), 7.5 (m), 7.9 (s).             33. 0.8 (s), 4.0 (m), 4.2 (s), 5.3 (m), 5.9 (m), 7.1 (m), 7.5 (m), 8.4         (s), 10.3 (br s).                                                              34. 0.7 (s), 1.3 (d), 4.1 (m), 4.2 (s), 7.1 (m), 7.5 (m), 8.4 (s), 10.1        (br d).                                                                        35. 0.7 (s), 4.8 (s), 7.0 (m), 7.4-7.7 (m), 7.9 (s), 8.0 (m).                  36. 0.7 (s), 3.7 (s), 4.0 (s), 7.1 (t), 7.5 (m), 7.8 (s), 10.8 (br.s).         37. 0.7 (s), 2.3 (s), 4.0 (two s), 7.1 (t), 7.5 (m), 7.7 (s).                  38. 0.7 (s), 2.1 (s), 4.7 (s), 7.1 (t), 7.5 (m), 7.8 (s), 7.9 (s).             39. 0.7 (s), 3.7 (s), 3.8 (s), 4.8 (s), 6.5 (br s), 7.0 (m), 7.4 (m), 7.8      (s).                                                                           40. 0.7 (s), 0.8 (s), 1.1 (d), 1.4 (s), 2.2 (m), 2.5 (m), 3.0 (t), 4.7         (ABq), 7.0 (t), 7.2 (m), 7.5 (m), 7.8 (s).                                     41. 0.7 (s), 1.1 (d), 2.1 (m), 2.7 (m), 4.6 (s), 5.0 (m), 5.7 (m), 6.9         (d), 7.0 (t), 7.5 (m), 7.8 (s).                                                42. 0.8 (s), 2.3 (s), 4.4 (s), 4.6 (s), 7.1 (m), 7.5 (m), 7.8 (s).             43. 0.7 (s), 3.6 (s), 4.0 (s), 4.1 (s), 4.2 (q), 7.1 (t), 7.5 (m), 7.7         (s), 12.1 (br. s).                                                             44. 0.7 (s), 1.7 (d), 4.1 (s), 4.3 (q), 7.1 (m), 7.5 (m), 7.9 (s).             45. 0.7 (s), 1.0 (d), 3.0 (heptet), 4.7 (s), 5.9 (s), 6.1 (s), 7.0 (t),        7.5 (m), 7.8 (s).                                                              46. 0.7 (s), 4.2 (s), 5.5 (dd), 6.4 (m), 7.1 (m), 7.5 (m), 7.9 (s).       

                                      TABLE II                                     __________________________________________________________________________      ##STR149##                                                                    Cmpd.                                                                          No. R.sub.1     R.sub.2                                                                              R.sub.3                                                                             X                                                   __________________________________________________________________________         4-FPh       4-FPh Me   vinyl                                                   4-FPh       4-FPh Me   ethynyl                                                 4-FPh       4-FPh Me   F                                                       4-FPh       4-FPh Me   Cl                                                      4-FPh       4-FPh Me   I                                                       4-FPh       4-FPh Me   NO.sub.2                                                4-FPh       4-FPh Me   NH.sub.2                                                4-FPh       4-FPh Me   Me.sub.2 N                                              4-FPh       4-FPh Me   SH                                                      4-FPh       4-FPh Me   SS                                                      4-FPh       4-FPh Me   SMe                                                     4-FPh       4-FPh Me   S(O)Me                                                  4-FPh       4-FPh Me   SO.sub.2 Me                                             4-FPh       4-FPh Me   SCCl.sub.3                                              4-FPh       4-FPh Me   SCH.sub.2 SCN                                           4-FPh       4-FPh Me   S(O)CH.sub.2 SCN                                        4-FPh       4-FPh Me   SO.sub.2 CH.sub.2 SCN                                   4-FPh       4-FPh Me   SCH.sub.2 CN                                            4-FPh       4-FPh Me   S(O)CH.sub.2 CN                                         4-FPh       4-FPh Me   SO.sub.2 CH.sub.2 CN                                    4-FPh       4-FPh Me   SCH.sub.2 CO.sub.2 Me                                   4-FPh       4-FPh Me   S(O)CH.sub.2 CO.sub.2 Me                                4-FPh       4-FPh Me   SO.sub.2 CH.sub.2 CO.sub.2 Me                           4-FPh       4-FPh Me   SCH.sub.2 CCH                                           4-FPh       4-FPh Me   SO.sub.2 CH.sub.2 CCH                                   4-FPh       4-FPh Me   SSMe                                                    4-FPh       4-FPh Me   SNH.sub.2                                               4-FPh       4-FPh Me   SNHMe                                                   4-FPh       4-FPh Me   SNMe.sub.2                                              4-FPh       4-FPh Me   SeH                                                     4-FPh       4-FPh Me   SeSe                                                    4-FPh       4-FPh Me   NHNH.sub.2                                              4-FPh       4-FPh Me                                                                                   ##STR150##                                             4-FPh       4-FPh Me                                                                                   ##STR151##                                             4-FPh       4-FPh Me                                                                                   ##STR152##                                             4-FPh       4-FPh Me                                                                                   ##STR153##                                             4-FPh       4-FPh Me                                                                                   ##STR154##                                             4-FPh       4-FPh Me                                                                                   ##STR155##                                             4-FPh       4-FPh Me                                                                                   ##STR156##                                             4-FPh       4-FPh Me   MeNC(OMe)S                                              4-FPh       4-FPh Me   CH(OH)vinyl                                         89. 4-FPh       4-FPh Me   CH(OH)CHCHCH.sub.3                                                                         m.p. 90-92°                          4-FPh       4-FPh Me   CH(OH)CHCHPh                                            4-FPh       4-FPh Me   CH(OH)4-ClPh                                            4-FPh       4-FPh Me   CHO                                                     4-FPh       4-FPh Me   CO .sub.-i-Pr                                           4-FPh       4-FPh Me   COCHCH.sub.2                                            4-FPh       4-FPh Me   COCHCHCH.sub.3                                          4-FPh       4-FPh Me   COCHCHPh                                                4-FPh       4-FPh Me   COPh                                                    4-FPh       4-FPh Me   CO4-ClPh                                                4-FPh       4-FPh Me   PO(OEt).sub.2                                           4-FPh       4-FPh Me   CONHMe                                                  4-FPh       4-FPh Me   CONHPh                                                  4-FPh       4-FPh Me   CONH -n-Bu                                              4-FPh       4-FPh Me   CSNHMe                                                  4-FPh       4-FPh Me   CSNH -n-Bu                                              4-FPh       4-FPh Me   CO.sub.2 Me                                             4-FPh       4-FPh Me   CS.sub.2 Me                                             4-FPh       4-FPh Me   COSMe                                                   4-FPh       Ph    Me   SH                                                      Ph          Ph    Me   SH                                                      4-ClPh      4-ClPh                                                                               Me   SH                                                      4-ClPh      Ph    Me   SH                                                      4-FPh       2-FPh Me   SH                                                      4-FPh       2,4-F.sub.2Ph                                                                        Me   SH                                                      4-FPh       4-FPh vinyl                                                                               SH                                                      4-FPh       4-FPh allyl                                                                               SH                                                      4-PhPh      Me    Me   SH                                                      4-PhPh      vinyl vinyl                                                                               SH                                                      4-FPh       4-FPh OH   SH                                                      4-FPh       4-FPh O .sub.-t-Bu                                                                        SH                                                      4-FPh       4-FPh Et   SH                                                      2,4-Cl.sub.2Ph                                                                             Me    Me   SH                                                       ##STR157## 4-FPh Me   SH                                                      4-FPh       Ph    Me   SS                                                      Ph          Ph    Me   SS                                                      4-ClPh      4-Cl Ph                                                                              Me   SS                                                      4-ClPh      Ph    Me   SS                                                      4-FPh       2-FPh Me   SS                                                      4-FPh       2,4-F.sub.2Ph                                                                        Me   SS                                                      4-FPh       4-FPh vinyl                                                                               SS                                                      4-FPh       4-FPh allyl                                                                               SS                                                      4-PhPh      Me    Me   SS                                                      4-PhPh      vinyl vinyl                                                                               SS                                                      4-FPh       4-FPh OH   SS                                                      4-FPh       4-FPh O .sub.-t-Bu                                                                        SS                                                      4-FPh       4-FPh Et   SS                                                      2,4-Cl.sub.2Ph                                                                             Me    Me   SS                                                       ##STR158## 4-FPh Me   SS                                                      4-FPh       Ph    Me   SSMe                                                    Ph          Ph    Me   SSMe                                                    4-ClPh      4-ClPh                                                                               Me   SSMe                                                    4-ClPh      Ph    Me   SSMe                                                    4-FPh       2-FPh Me   SSMe                                                    4-FPh       2,4-F.sub.2Ph                                                                        Me   SSMe                                                    4-FPh       4-FPh vinyl                                                                               SSMe                                                    4-FPh       4-FPh allyl                                                                               SSMe                                                    4-PhPh      Me    Me   SSMe                                                    4-PhPh      vinyl vinyl                                                                               SSMe                                                    4-FPh       4-FPh OH   SSMe                                                    4-FPh       4-FPh O .sub.-t-Bu                                                                        SSMe                                                    4-FPh       4-FPh Et   SSMe                                                    2,4-Cl.sub.2Ph                                                                             Me    Me   SSMe                                                     ##STR159## 4-FPh Me   SSMe                                                    4-FPh       Ph    Me                                                                                   ##STR160##                                             Ph          Ph    Me                                                                                   ##STR161##                                             4-ClPh      4-ClPh                                                                               Me                                                                                   ##STR162##                                             4-ClPh      Ph    Me                                                                                   ##STR163##                                             4-FPh       2-FPh Me                                                                                   ##STR164##                                             4-FPh       2,4-F.sub.2Ph                                                                        Me                                                                                   ##STR165##                                             4-FPh       4-FPh vinyl                                                                                ##STR166##                                             4-FPh       4-FPh allyl                                                                                ##STR167##                                             4-PhPh      Me    Me                                                                                   ##STR168##                                             4-PhPh      vinyl vinyl                                                                                ##STR169##                                             4-FPh       4-FPh OH                                                                                   ##STR170##                                             4-FPh       4-FPh O .sub.-t-Bu                                                                         ##STR171##                                             4-FPh       4-FPh Et                                                                                   ##STR172##                                             2,4-Cl.sub.2Ph                                                                             Me    Me                                                                                   ##STR173##                                              ##STR174## 4-FPh Me                                                                                   ##STR175##                                             4-FPh       Ph    Me   CHO                                                     Ph          Ph    Me   CHO                                                     4-ClPh      4-ClPh                                                                               Me   CHO                                                     4-ClPh      Ph    Me   CHO                                                     4-FPh       2-FPh Me   CHO                                                     4-FPh       2,4-F.sub.2Ph                                                                        Me   CHO                                                     4-FPh       4-FPh vinyl                                                                               CHO                                                     4-FPh       4-FPh allyl                                                                               CHO                                                     4-PhPh      Me    Me   CHO                                                     4-PhPh      vinyl vinyl                                                                               CHO                                                     4-FPh       4-FPh OH   CHO                                                     4-FPh       4-FPh O -t-Bu                                                                             CHO                                                     4-FPh       4-FPh Et   CHO                                                     2,4-Cl.sub.2Ph                                                                             Me    Me   CHO                                                      ##STR176## 4-FPh Me   CHO                                                 __________________________________________________________________________

                                      TABLE III                                    __________________________________________________________________________      ##STR177##                                                                    Cmpd.                                                                          No. R.sub.1     R.sub.2   R.sub.3  Y                                           __________________________________________________________________________         4-FPh       4-FPh     Me       F                                               4-FPh       4-FPh     Me       Cl                                              4-FPh       4-FPh     Me       Br                                              4-FPh       4-FPh     Me       I                                           90. 4-FPh       4-FPh     Me       NH.sub.2   m.p. 116-117°             91. 4-FPh       4-FPh     Me       NH.sub.3.sup.+ Cl.sup.-                                                                   m.p. 191-194°             92. 4-FPh       4-FPh     Me       SH         m.p. 164-165°             93. 4-FPh       4-FPh     Me       SS         oil.sup.1                        94. 4-FPh       4-FPh     Me       SMe        oil.sup.2                            4-FPh       4-FPh     Me       S(O)Me                                          4-FPh       4-FPh     Me       SO.sub.2 Me                                     4-FPh       4-FPh     Me       SEt                                             4-FPh       4-FPh     Me       S(O)Et                                          4-FPh       4-FPh     Me       SO.sub.2 Et                                     4-FPh       4-F Ph    Me       S -n-Pr                                         4-FPh       4-FPh     Me       S(O) -n-Pr                                      4-FPh       4-FPh     Me       SO.sub.2 -n-Pr                                  4-FPh       4-FPh     Me       SCH.sub.2 CHMe.sub.2                            4-FPh       4-FPh     Me       S(O)CH.sub.2 CHMe.sub.2                         4-FPh       4-FPh     Me       SO.sub.2 CH.sub.2 CHMe.sub.2                    4-FPh       4-FPh     Me       SCH.sub.2 CHCH.sub.2                            4-FPh       4-FPh     Me       S(O)CH.sub.2 CHCH.sub.2                         4-FPh       4-FPh     Me       SO.sub.2 CH.sub.2 CHCH.sub.2                95. 4-FPh       4-FPh     Me       SCH.sub.2 SCN                                                                             oil.sup.3                            4-FPh       4-FPh     Me       S(O)CH.sub.2 SCN                            96. 4-FPh       4-FPh     Me       SO.sub.2 CH.sub.2 SCN                                                                     oil.sup.4                            4-FPh       4-FPh     Me       SCH.sub.2 CN                                    4-FPh       4-FPh     Me       S(O)CH.sub.2 CN                                 4-FPh       4-FPh     Me       SO.sub.2 CH.sub.2 CN                            4-FPh       4-FPh     Me       SSMe                                            4-FPh       4-FPh     Me       SSEt                                            4-FPh       4-FPh     Me       SS -n-Pr                                        4-FPh       4-FPh     Me       SS .sub.- i-Pr                                  4-FPh       4-FPh     Me       SS -n-Bu                                        4-FPh       4-FPh     Me       SSCH.sub.2 Ph                                   4-FPh       4-FPh     Me       SSCCl.sub.3                                     4-FPh       4-FPh     Me       SSPh                                            4-FPh       4-FPh     Me       SS4-FPh                                         4-FPh       4-FPh     Me       SS3-CF.sub.3Ph                                  4-FPh       4-FPh     Me       SS4-MeOPh                                       4-FPh       4-FPh     Me                                                                                       ##STR178##                                     4-FPh       4-FPh     Me                                                                                       ##STR179##                                     4-FPh       4-FPh     Me                                                                                       ##STR180##                                     4-FPh       4-FPh     Me                                                                                       ##STR181##                                     4-FPh       4-FPh     Me                                                                                       ##STR182##                                     4-FPh       4-FPh     Me                                                                                       ##STR183##                                     4-FPh       4-FPh     Me                                                                                       ##STR184##                                     4-FPh       4-FPh     Me                                                                                       ##STR185##                                     4-FPh       4-FPh     Me                                                                                       ##STR186##                                     4-FPh       4-FPh     Me                                                                                       ##STR187##                                     4-FPh       4-FPh     Me                                                                                       ##STR188##                                     4-FPh       4-FPh     Me                                                                                       ##STR189##                                     4-FPh       4-FPh     Me                                                                                       ##STR190##                                     4-FPh       4-FPh     Me                                                                                       ##STR191##                                     4-FPh       4-FPh     Me                                                                                       ##STR192##                                     4-FPh       4-FPh     Me                                                                                       ##STR193##                                     4-FPh       4-FPh     Me                                                                                       ##STR194##                                     4-FPh       4-FPh     Me                                                                                       ##STR195##                                     4-FPh       4-FPh     Me                                                                                       ##STR196##                                     4-FPh       4-FPh     Me                                                                                       ##STR197##                                     4-FPh       4-FPh     Me                                                                                       ##STR198##                                     4-F Ph      4-FPh     Me                                                                                       ##STR199##                                     4-FPh       4-FPh     Me                                                                                       ##STR200##                                     4-FPh       4-FPh     Me                                                                                       ##STR201##                                     4-FPh       4-FPh     Me                                                                                       ##STR202##                                     4-FPh       4-FPh     Me                                                                                       ##STR203##                                     4-FPh       4-FPh     Me                                                                                       ##STR204##                                     4-FPh       4-FPh     Me                                                                                       ##STR205##                                     4-FPh       4-FPh     Me                                                                                       ##STR206##                                     4-FPh       4-FPh     Me                                                                                       ##STR207##                                     4-FPh       4-FPh     Me       CHO                                             4-FPh       4-FPh     Me       CO.sub.2 Me                                     4-FPh       Ph        Me       SH                                              Ph          Ph        Me       SH                                              4-ClPh      4-ClPh    Me       SH                                              4-FPh       2-FPh     Me       SH                                              4-FPh       2,4-F.sub.2Ph                                                                            Me       SH                                              4-FPh       4-FPh     vinyl    SH                                              4-FPh       4-FPh     allyl    SH                                              4-PhPh      Me        Me       SH                                              4-PhPh      vinyl     vinyl    SH                                              4-FPh       4-FPh     OH       SH                                              4-FPh       4-FPh     O .sub.-t-Bu                                                                            SH                                              4-FPh       4-FPh     Er       SH                                              2,4-Cl.sub.2Ph                                                                             Me        Me       SH                                               ##STR208## 4-FPh     Me       SH                                              4-FPh       Ph        Me       SS                                              Ph          Ph        Me       SS                                              4-ClPh      4-ClPh    Me       SS                                              4-ClPh      Ph        Me       SS                                              4-FPh       2-FPh     Me       SS                                              4-FPh       2,4-F.sub.2Ph                                                                            ME       SS                                              4-FPh       4-FPh     vinyl    SS                                              4-FPh       4-FPh     allyl    SS                                              4-PhPh      Me        Me       SS                                              4-PhPh      vinyl     vinyl    SS                                              4-FPh       4-FPh     OH       SS                                              4-FPh       4-FPh     O .sub.-t-Bu                                                                            SS                                              4-FPh       4-FPh     Et       SS                                              2,4-Cl.sub.2Ph                                                                             Me        Me       SS                                               ##STR209## 4-FPh     Me       SS                                              4-FPh       Ph        Me       SMe                                             Ph          Ph        ME       SMe                                             4-ClPh      4-ClPh    Me       SMe                                             4-ClPh      Ph        Me       SMe                                             4-FPh       2-FPh     Me       SMe                                             4-FPh       2,4-F.sub.2Ph                                                                            Me       SMe                                             4-FPh       4-FPh     vinyl    SMe                                             4-FPh       4-FPh     allyl    SMe                                             4-PhPh      Me        Me       SMe                                             4-PhPh      vinyl     vinyl    SMe                                             4-FPh       4-FPh     OH       SMe                                             4-FPh       4-FPh     O .sub.-t-Bu                                                                            SMe                                             4-FPh       4-FPh     Et       SMe                                             2,4-Cl.sub.2Ph                                                                             Me        Me       SMe                                              ##STR210## 4-FPh     Me       SMe                                             4-FPh       Ph        Me       S(O)Me                                          Ph          Ph        Me       S(O)Me                                          4-ClPh      4-ClPh    Me       S(O)Me                                          4-ClPh      Ph        Me       S(O)Me                                          4-FPh       2-FPh     Me       S(O)Me                                          4-FPh       2,4-F.sub.2Ph                                                                            Me       S(O)Me                                          4-FPh       4-FPh     vinyl    S(O)Me                                          4-FPh       4-FPh     allyl    S(O)Me                                          4-PhPh      Me        Me       S(O)Me                                          4-PhPh      vinyl     vinyl    S(O)Me                                          4-FPh       4-FPh     OH       S(O)Me                                          4-FPh       4-FPh     O .sub.-t-Bu                                                                            S(O)Me                                          4-FPh       4-FPh     Et       S(O)Me                                          2,4-Cl.sub.2Ph                                                                             Me        Me       S(O)Me                                           ##STR211## 4-FPh     Me       S(O)Me                                          4-FPh       Ph        Me       SO.sub.2 Me                                     Ph          Ph        Me       SO.sub.2 Me                                     4-ClPh      4-ClPh    Me       SO.sub.2 Me                                     4-ClPh      Ph        Me       SO.sub.2 Me                                     4-FPh       2-FPh     Me       SO.sub.2 Me                                     4-FPh       2,4-F.sub.2Ph                                                                            Me       SO.sub.2 Me                                     4-FPh       4-FPh.sub.2                                                                              vinyl    SO.sub.2 Me                                     4-FPh       4-FPh.sub.2                                                                              allyl    SO.sub.2 Me                                     4-PhPh      Me        Me       SO.sub.2 Me                                     4-PhPh      vinyl.sub.2.sup.2                                                                        vinyl    SO.sub.2 Me                                     4-FPh       4-FPh.sub.2                                                                              OH       SO.sub.2 Me                                     4-FPh       4-FPh.sub.2                                                                              O .sub.-t-Bu                                                                            SO.sub.2 Me                                     4-FPh       4-FPh     Et       SO.sub.2 Me                                     2,4-Cl.sub.2Ph                                                                             Me        Me       SO.sub.2 Me                                      ##STR212## 4-FPh     Me       SO.sub.2 Me                                     4-FPh       Ph        Me       SSMe                                            Ph          Ph        Me       SSMe                                            4-ClPh      4-ClPh    Me       SSMe                                            4-FPh       2-FPh     Me       SSMe                                            4-FPh       2,4-F.sub.2Ph                                                                            Me       SSMe                                            4-FPh       4-FPh     vinyl    SSMe                                            4-FPh       4-FPh     allyl    SSMe                                            4-PhPh      Me        Me       SSMe                                            4-PhPh      vinyl     vinyl    SSMe                                            4-FPh       4-FPh     OH       SSMe                                            4-FPh       4-FPh     O .sub.-t-Bu                                                                            SSMe                                            4-FPh       4-FPh     Et       SSMe                                            2,4-Cl.sub.2Ph                                                                             Me        Me       SSMe                                             ##STR213## 4-FPh     Me       SSMe                                            4-FPh       Ph        Me                                                                                       ##STR214##                                     Ph          Ph        Me                                                                                       ##STR215##                                     4-ClPh      4-ClPh    Me                                                                                       ##STR216##                                     4-ClPh      Ph        Me                                                                                       ##STR217##                                     4-FPh       2-FPh     Me                                                                                       ##STR218##                                     4-FPh       2,4-F.sub.2Ph                                                                            Me                                                                                       ##STR219##                                     4-FMe       4-FPh     vinyl                                                                                    ##STR220##                                     4-FPh       4-FPh     allyl                                                                                    ##STR221##                                     4-PhPh      Me        Me                                                                                       ##STR222##                                     4-PhPh      vinyl     vinyl                                                                                    ##STR223##                                     4-FPh       4-FPh     OH                                                                                       ##STR224##                                     4-FPh       4-FPh     O .sub.-t-Bu                                                                             ##STR225##                                     4-FPh       4-FPh     Et                                                                                       ##STR226##                                     2,4-Cl.sub.2Ph                                                                             Me        Me                                                                                       ##STR227##                                      ##STR228## 4-FPh     Me                                                                                       ##STR229##                                     4-FPh       Ph        Me                                                                                       ##STR230##                                     Ph          Ph        Me                                                                                       ##STR231##                                     4-ClPh      4-ClPh    Me                                                                                       ##STR232##                                     4-ClPh      Ph        Me                                                                                       ##STR233##                                     4-FPh       2-FPh     Me                                                                                       ##STR234##                                     4-FPh       2,4-F.sub.2Ph                                                                            Me                                                                                       ##STR235##                                     4-FPh       4-FPh     vinyl                                                                                    ##STR236##                                     4-FPh       4-FPh     allyl                                                                                    ##STR237##                                     4-PhPh      Me        Me                                                                                       ##STR238##                                     4-PhPh      vinyl     vinyl                                                                                    ##STR239##                                     4-FPh       4-FPh     OH                                                                                       ##STR240##                                     4-FPh       4-FPh     O .sub.-t-Bu                                                                             ##STR241##                                     4-FPh       4-FPh     Et                                                                                       ##STR242##                                     2,4-ClPh    Me        Me                                                                                       ##STR243##                                      ##STR244## 4-FPh     Me                                                                                       ##STR245##                                     4-FPh       Ph        Me                                                                                       ##STR246##                                     Ph          Ph        Me                                                                                       ##STR247##                                     4-ClPh      4-ClPh    Me                                                                                       ##STR248##                                     4-ClPh      Ph        Me                                                                                       ##STR249##                                     4-FPh       2-FPh     Me                                                                                       ##STR250##                                     4-FPh       2,4-F.sub.2Ph                                                                            Me                                                                                       ##STR251##                                     4-FPh       4-FPh     vinyl                                                                                    ##STR252##                                     4-FPh       4-FPh     allyl                                                                                    ##STR253##                                     4-PhPh      Me        Me                                                                                       ##STR254##                                     4-PhPh      vinyl     vinyl                                                                                    ##STR255##                                     4-FPh       4-FPh     OH                                                                                       ##STR256##                                     4-FPh       4-FPh     O .sub.-t-Bu                                                                             ##STR257##                                     4-FPh       4-FPh     Et                                                                                       ##STR258##                                     2,4-Cl.sub.2Ph                                                                             Me        Me                                                                                       ##STR259##                                      ##STR260## 4-FPh     Me                                                                                       ##STR261##                                     4-FPh       Ph        Me       F                                               Ph          Ph        Me       F                                               4-ClPh      4-ClPh    Me       F                                               4-ClPh      Ph        Me       F                                               4-FPh       2-FPh     Me       F                                               4-FPh       2,4-F.sub.2Ph                                                                            Me       F                                               4-FPh       4-FPh     vinyl    F                                               4-FPh       4-FPh     allyl    F                                               4-PhPh      Me        Me       F                                               4-PhPh      vinyl     vinyl    F                                               4-FPh       4-FPh     OH       F                                               4-FPh       4-FPh     O .sub.-t-Bu                                                                            F                                               4-FPh       4-FPh     Et       F                                               2,4-Cl.sub.2Ph                                                                             Me        Me       F                                                ##STR262## 4-FPh     Me       F                                               4-FPh       Ph        Me       Cl                                              Ph          Ph        Me       Cl                                              4-ClPh      4-ClPh    Me       Cl                                              4-ClPh      Ph        Me       Cl                                              4-FPh       2-FPh     Me       Cl                                              4-FPh       2,4-F.sub.2Ph                                                                            Me       Cl                                              4-FPh       4-FPh     vinyl    Cl                                              4-FPh       4-FPh     allyl    Cl                                              4-PhPh      Me        Me       Cl                                              4-PhPh      vinyl     vinyl    Cl                                              4-FPh       4-FPh     OH       Cl                                              4-FPh       4-FPh     O  .sub.-t-Bu                                                                           Cl                                              4-FPh       4-FPh     Et       Cl                                              2,4-Cl.sub.2Ph                                                                             Me        Me       Cl                                               ##STR263## 4-FPh     Me       Cl                                              4-FPh       Ph        Me       CHO                                             Ph          Ph        Me       CHO                                             4-ClPh      4-ClPh    Me       CHO                                             4-ClPh      Ph        Me       CHO                                             4-FPh       2-FPh     Me       CHO                                             4-FPh       2,4-F.sub.2Ph                                                                            Me       CHO                                             4-FPh       4-FPh     vinyl    CHO                                             4-FPh       4-FPh     allyl    CHO                                             4-PhPh      Me        Me       CHO                                             4-PhPh      vinyl     vinyl    CHO                                             4-FPh       4-FPh     OH       CHO                                             4-FPh       4-FPh     O .sub.-t-Bu                                                                            CHO                                             4-FPh       4-FPh     Et       CHO                                             2,4-Cl.sub.2Ph                                                                             Me        Me       CHO                                              ##STR264## 4-FPh     Me       CHO                                             PhCHCH      CH.sub.3  CH.sub.3 SH                                              4-FPhCHCH   4-FPh     CH.sub.3 SH                                              (CH.sub.3).sub.2 CCH.sub.2                                                                 2,4-F.sub.2Ph                                                                            CH.sub.3 SH                                              CH.sub.2C(Et)                                                                              4-ClPh    CH.sub.3 SH                                              1-naphthyl  2-CF.sub.3Ph                                                                             CH.sub.3 SH                                              2-naphthyl  CH.sub.3  CH.sub.3 SH                                              PhCC        4-FPh     4-FPh    SH                                               -n-BucC    4-FPh     CH.sub.3 SH                                              CH.sub.3 CC 4-FPh     4-FPh    SH                                              4-PhPh      CH.sub.2 CHC(CH.sub.3).sub.2                                                             O .sub.-t-Bu                                                                            SH                                              4-FPh       3-CF.sub.3Ph                                                                             Me       SH                                              4-MeOPh     4-ClPh     -n-Bu   SH                                              4-(4-FPh)pH vinyl     O .sub.-t-Bu                                                                            SH                                              4-CHF.sub.2 OPh                                                                            Ph        Me       SH                                              4-BrPh       -n-hexyl Me       SH                                              4-MePh      4-MePh    Me       SH                                              4-CF.sub.3 OPh                                                                             4-CF.sub.3 OPh                                                                           Me       SH                                              4-( -n-Bu)Ph                                                                               4-FPh     Me       SH                                              2,4-Cl.sub.2Ph                                                                             CH.sub.2 C(Me)CH.sub.2                                                                   CH.sub.2 C(Me)CH.sub.2                                                                  SH                                              4-FPh       4-FPh     O -n-Bu  SH                                                .sub.-t-BuCC                                                                             4-FPh     Me       SH                                              2,6-MeO.sub.2Ph                                                                            Me        Me       SH                                              4-( .sub.-t-Bu)Ph                                                                          Me        Me       SH                                               ##STR265## 4-FPh     Me       SH                                              PhCHCH      CH.sub.3  CH.sub.3 SS                                              4-FPhCHCH   4-FPh     CH.sub.3 SS                                              (CH.sub.3).sub.2 CCH.sub.2                                                                 2,4-F.sub.2Ph                                                                            CH.sub.3 SS                                              CH.sub.2C(Et)                                                                              4-ClPh    CH.sub.3 SS                                              1-naphthyl  2-CF.sub.3Ph                                                                             CH.sub.3 SS                                              2-naphthyl  CH.sub.3  CH.sub.3 SS                                              PhCC        4-FPh     4-FPh    SS                                               -n-BuCC    4-FPh     CH.sub.3 SS                                              CH.sub.3 CC 4-FPh     4-FPh    SS                                              4-PhPh      CH.sub.2 CHC(CH.sub.3).sub. 2                                                            O .sub.-t-Bu                                                                            SS                                              4-FPh       3-CF.sub.3Ph                                                                             Me       SS                                              4-MeOPh     4-ClPh     -n-Bu   SS                                              4-(4-FPh)Ph vinyl     O .sub.-t-Bu                                                                            SS                                              4-CHF.sub.2 OPh                                                                            Ph        Me       SS                                              4-BrPh       -n-hexyl Me       SS                                              4-MePh      4-MePh    Me       SS                                              4-CF.sub.3 OPh                                                                             4-CF.sub.3 OPh                                                                           Me       SS                                              4-( -n-Bu)Ph                                                                               4-FPh     Me       SS                                              2,4-Cl.sub.2Ph                                                                             CH.sub.2 C(Me)CH.sub.2                                                                   CH.sub.2 C(Me)CH.sub.2                                                                  SS                                              4-FPh       4-FPh     O -n-Bu  SS                                               .sub.-t-BuCC                                                                              4-FPh     Me       SS                                              2,6-MeO.sub.2Ph                                                                            Me        Me       SS                                              4-( .sub.-t-Bu)Ph                                                                          Me        Me       SS                                               ##STR266## 4-FPh     Me       SS                                              PhCHCH      CH.sub.3  CH.sub.3                                                                                 ##STR267##                                     4-FPhCHCH   4-FPh     CH.sub.3                                                                                 ##STR268##                                     (CH.sub.3).sub.2 CCH.sub.2                                                                 2,4-F.sub.2Ph                                                                            CH.sub.3                                                                                 ##STR269##                                     CH.sub.2C(Et)                                                                              4-ClPh    CH.sub.3                                                                                 ##STR270##                                     1-naphthyl  2-CF.sub.3Ph                                                                             CH.sub.3                                                                                 ##STR271##                                     2-naphthyl  CH.sub.3  CH.sub.3                                                                                 ##STR272##                                     PhCC        4-FPh     4-FPh                                                                                    ##STR273##                                     BuCC        4-FPh     CH.sub.3                                                                                 ##STR274##                                     CH.sub.3 CC 4-FPh     4-FPh                                                                                    ##STR275##                                     4-PhPh      CH.sub.2 CHC(CH.sub.3).sub.2                                                             O .sub.-t-Bu                                                                             ##STR276##                                     4-FPh       3-CF.sub.3Ph                                                                             Me                                                                                       ##STR277##                                     4-MeOPh     4-ClPh     -n-Bu                                                                                   ##STR278##                                     4-(4-FPh)Ph vinyl     O .sub.-t-Bu                                                                             ##STR279##                                     4-CHF.sub.2 OPh                                                                            Ph        Me                                                                                       ##STR280##                                     4-BrPh       -n-hexyl Me                                                                                       ##STR281##                                     4-MePh      4-MePh    Me                                                                                       ##STR282##                                     4-CF.sub.3 OPh                                                                             4-CF.sub.3 OPh                                                                           Me                                                                                       ##STR283##                                     4-( -n-Bu)Ph                                                                               4-FPh     Me                                                                                       ##STR284##                                     2,4-Cl.sub.2Ph                                                                             CH.sub.2 C(Me)CH.sub.2                                                                   CH.sub.2 C(Me)CH.sub.2                                                                   ##STR285##                                     4-FPh       4-FPh     O -n-Bu                                                                                  ##STR286##                                     t-BuCC      4-FPh     Me                                                                                       ##STR287##                                     2,6-MeO.sub.2Ph                                                                            Me        Me                                                                                       ##STR288##                                     4-( .sub.-t-Bu)Ph                                                                          Me        Me                                                                                       ##STR289##                                      ##STR290## 4-FPh     Me                                                                                       ##STR291##                                 __________________________________________________________________________      Footnotes to Table III                                                         NMR Data (CDCl.sub.3): peak position in parts per million downfield from       tetramethylsilane.                                                             1. 0.7 (s), 4.1 (s), 7.1 (m), 7.4 (m), 7.7 (s).                                2. 0.7 (s), 2.5 (s), 4.1 (s), 7.1 (m), 7.5 (m), 7.7 (s).                       3. 0.7 (s), 4.2 (s), 4.6 (s), 7.1 (m), 7.4 (m), 7.8 (s).                       4. 0.7 (s), 4.3 (s), 4.4 (s), 7.1 (m), 7.5 (m), 7.9 (s).            T2         TABLE IV-? -      ##STR292##

                                      TABLE V                                      __________________________________________________________________________     Cmpd.                                                                          No. R.sub.1     R.sub.2                                                                              R.sub.3                                                                             X                                                   __________________________________________________________________________     97. 4-FPh       4-FPh Me   I        oil.sup.1                                  98. 4-FPh       4-FPh Me   SH       m.p. 130-139°                           4-FPh       4-FPh Me   SS                                                  99. 4-FPh       4-FPh Me   SO.sub.2 OH                                                                             m.p. 208-218°                           4-FPh       4-FPh Me   SEt                                                     4-FPh       4-FPh Me   SPr                                                     4-FPh       4-FPh Me   S .sub.-i-Pr                                            4-FPh       4-FPh Me   SBu                                                     4-FPh       4-FPh Me   SCH.sub.2 CHMe.sub.2                                    4-FPh       4-FPh Me   SCH(Me)Et                                               4-FPh       4-FPh Me   SCMe.sub.3                                              4-FPh       4-FPh Me   SCH.sub.2 CN                                            4-FPh       4-FPh Me   SCH.sub.2 SCN                                           4-FPh       4-FPh Me   S(O)Et                                                  4-FPh       4-FPh Me   S(O)Pr                                                  4-FPh       4-FPh Me   S(O) .sub.-i-Pr                                         4-FPh       4-FPh Me   S(O)Bu                                                  4-FPh       4-FPh Me   S(O)CH.sub.2 CHMe.sub.2                                 4-FPh       4-FPh Me   S(O)CH(Me)Et                                            4-FPh       4-FPh Me   S(O)CMe.sub.3                                           4-FPh       4-FPh Me   S(O)CH.sub.2 CN                                         4-FPh       4-FPh Me   S(O)CH.sub.2 SCN                                        4-FPh       4-FPh Me   SO.sub.2 Et                                             4-FPh       4-FPh Me   SO.sub.2 Pr                                             4-FPh       4-FPh Me   SO.sub.2 .sub.-i-Pr                                     4-FPh       4-FPh Me   SO.sub.2 Bu                                             4-FPh       4-FPh Me   SO.sub.2 CH.sub.2 CHMe.sub.2                            4-FPh       4-FPh Me   SO.sub.2 CH(Me)Et                                       4-FPh       4-FPh Me   SO.sub.2 CMe.sub.3                                      4-FPh       4-FPh Me   SO.sub.2 CH.sub.2 CN                                    4-FPh       4-FPh Me   SO.sub.2 CH.sub.2 SCN                                   4-FPh       Ph    Me   I                                                       Ph          Ph    Me   I                                                       4-ClPh      4-ClPh                                                                               Me   I                                                       4-ClPh      Ph    Me   I                                                       4-FPh       2-FPh Me   I                                                       4-FPh       2,4-F.sub.2Ph                                                                        Me   I                                                       4-FPh       4-FPh vinyl                                                                               I                                                       4-FPh       4-FPh allyl                                                                               I                                                       4-PhPh      Me    Me   I                                                       4-PhPh      vinyl vinyl                                                                               I                                                       4-FPh       4-FPh OH   I                                                       4-FPh       4-FPh O .sub.-t-Bu                                                                        I                                                       4-FPh       4-FPh Et   I                                                       2,4-Cl.sub.2Ph                                                                             Me    Me   I                                                        ##STR293## 4-FPh Me   I                                                       4-FPh       Ph    Me   SH                                                      Ph          Ph    Me   SH                                                      4-ClPh      4-ClPh                                                                               Me   SH                                                      4-ClPh      Ph    Me   SH                                                      4-FPh       2-FPh Me   SH                                                      4-FPh       2,4-F.sub.2Ph                                                                        Me   SH                                                      4-FPh       4-FPh vinyl                                                                               SH                                                      4-FPh       4-FPh allyl                                                                               SH                                                      4-PhPh      Me    Me   SH                                                      4-PhPh      vinyl vinyl                                                                               SH                                                      4-FPh       4-FPh OH   SH                                                      4-FPh       4-FPh O .sub.-t-Bu                                                                        SH                                                      4-FPh       4-FPh Et   SH                                                      2,4-Cl Ph   Me    Me   SH                                                       ##STR294## 4-FPh Me   SH                                                  __________________________________________________________________________      Footnotes to Table V                                                           NMR Data (CDCl.sub.3): peak position in parts per million downfield from       tetramethylsilane.                                                             .sup.1 0.6 (s), 4.0 (s), 6.6 (s), 7.0 (s), 7.1 (m), 7.4 (m).             

Utility

The compounds of this invention are useful as plant disease control agents. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, vegetable, field, cereal and fruit crops, such as, Puccinia recondita, Sphaerotheca fuliginea, Erysiphe graminis, Podosphaera leucotricha, Venturia inaequalis, Pyricularia oryzae, Bipolaris oryzae, Cercospora arachidicola, Cercospora beticola and Monilinia fructicola. They also control soil borne pathogens such as Rhizoctonia solani.

Formulation

The compounds of this invention will generally be used in formulations with a liquid or solid diluent or with an organic solvent. Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly. Sprayable formulations may be extended in suitable media and used at spray volumes of from about one to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain about 1% to 99% by weight of active ingredient(s) and at least one of (a) about 0.1% to 35% surfactant(s) and (b) about 5% to 99% solid or liquid inert diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:

    ______________________________________                                                     Active  Percent by Weight                                                      Ingredient                                                                             Diluent(s)                                                                               Surfactant(s)                                    ______________________________________                                         Wettable Powders                                                                             20-90      0-74     1-10                                         Oil Suspensions,                                                                              5-50     40-95     0-35                                         Emulsions, Solutions,                                                          (including Emulsifiable                                                        Concentrates)                                                                  Aqueous Suspensions                                                                          10-50     40-84     1-20                                         Dusts          1-25     70-99     0-5                                          Granules and Pellets                                                                          1-95      5-99     0-15                                         High Strength 90-99      0-10     0-2                                          Compositions                                                                   ______________________________________                                    

Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.

Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, N.J. The more absorptive diluents are preferred for the wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide," 2nd Ed., Interscience, N.Y., 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0° C. "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, N.J., as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, etc. Preferably, ingredients should be approved by the U.S. Environmental Protection Agency for the use intended.

The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Pat. No. 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning, "Agglomeration", Chemical Engineering, Dec. 4, 1967, pp. 147ff. and "Perry's Chemical Engineer's Handbook", 4th Edn., McGraw-Hill, N.Y., 1963, pp. 8-59ff.

For further information regarding the art of formulation, see for example:

H. M. Loux, U.S. Pat. No. 3,235,361, Feb. 15, 1966, Col. 6, Line 16 through Col. 7, Line 19 and Examples 10 through 41.

R. W. Luckenbaugh, U.S. Pat. No. 3,309,192, Mar. 14, 1967, Col. 5, Line 43 through Col. 7, Line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167, 169-182.

H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, June 23, 1959, Col. 3, Line 66 through Col. 5, Line 17 and Examples 1-4.

G. C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pp. 81-96.

J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Edn. Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.

Examples of useful formulations of compounds of the present invention are as follows.

EXAMPLE 16 Wettable Powder

    ______________________________________                                         1-[bis(4-fluorophenyl)(methyl)silylmethyl]-1H--1,2,4-                                                       80%                                               triazole-5-thiol                                                               sodium alkylnaphthalenesulfonate                                                                            2%                                                sodium ligninsulfonate       2%                                                synthetic amorphous silica   3%                                                kaolinite                    13%                                               ______________________________________                                    

The ingredients are blended, hammer-milled, reblended and packaged.

EXAMPLE 17 High Strength Concentrate

    ______________________________________                                         1-[bis(4-fluorophenyl)(methyl)silylmethyl]-5-iodo-                                                         98.5%                                              1H--1,2,4-triazole                                                             silica aerogel              0.5%                                               synthetic amorphous fine silica                                                                            1.0%                                               ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produce a high strength concentrate essentially all passing a U.S.S. No. 50 sieve (0.3 mm openings). This material may then be formulated in a variety of ways.

EXAMPLE 18 Aqueous Suspension

    ______________________________________                                         1-[bis(4-fluorophenyl)(methyl)silylmethyl]-1H--1,2,4-                                                      25%                                                triazole-5-thiol                                                               hydrated attapulgite        3%                                                 crude calcium ligninsulfonate                                                                              10%                                                sodium dihydrogen phosphate 0.5%                                               water                       61.5%                                              ______________________________________                                    

The ingredients are ground together in a ball, sand, or roller mill until the solid particles have been reduced to diameters under 10 microns.

EXAMPLE 19 Solution

    ______________________________________                                         1-[bis(4-fluorophenyl)(methyl)silylmethyl]-2-iodo-                                                          30%                                               1H--imidazole                                                                  dimethylformamide            70%                                               ______________________________________                                    

The ingredients are combined and stirred to produce a solution, which can be used for low volume applications.

EXAMPLE 20 Emulsifiable Concentrate

    ______________________________________                                         1-[bis(4-fluorophenyl)(methyl)silylmethyl]-5-                                                               15%                                               (cyanomethylsulfonyl)-1H--1,2,4-triazole                                       blend of calcium sulfonates  25%                                               and nonionic surfactants                                                       xylene                       60%                                               ______________________________________                                    

The ingredients are combined and stirred until the active is dissolved. A fine screen filter is included in packaging operation to insure the absence of any extraneous undissolved material in the product.

EXAMPLE 21 Granule

    ______________________________________                                         wettable powder of Example 16                                                                        15%                                                      gypsum                69%                                                      potassium sulfate     16%                                                      ______________________________________                                    

The ingredients are blended in a rotating or fluid bed mixer and water sprayed on to accomplish granulation. When most of the material has reached the desired range of 1.0 to 0.42 mm. (U.S.S. No. 18 to 40 sieves), the granules are removed, dried, and screened. Oversize material is crushed to produce additional material in the desired range.

The compounds of this invention can be mixed with fungicides, bactericides, acaricides, nematicides, insecticides, or other biologically active compounds in order to achieve desired results with a minimum expenditure of time, effort and material. Amounts of these biologically active materials added for each part by weight of the composition of this invention may vary from 0.05 to 45 parts by weight. Suitable agents of this type are well-known to those skilled in the art. Some are listed below:

Fungicides:

methyl 2-benzimidazolecarbamate (carbendazim)

tetramethylthiuram disulfide (thiuram)

n-dodecylguanidine acetate (dodine)

manganese ethylenebisdithiocarbamate (maneb)

1,4-dichloro-2,5-dimethoxybenzene (chloroneb)

methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate (benomyl)

2-cyano-N-ethylcarbamoyl-2-methoxyiminoacetamide (cymoxanil)

N-trichloromethylthiotetrahydrophthalimide (captan)

N-trichloromethylthiophthalimide (folpet)

dimethyl(4,4'-o-phenylene)bis(3-thioallophanate) (thiophanate-methyl)

2-(thiazol-4-yl)benzimidazole (thiabendazole)

aluminum tris(O-ethyl phosphonate) ("Aliette")

tetrachloroisophthalonitrile (chlorothalonil)

2,6-dichloro-4-nitroaniline (dichloran)

N-(2,6-dimethylphenyl)-N-(methoxyacetyl)alanine methyl ester (metalaxyl)

cis-N-[(1,1,2,2-tetrachloroethyl)thio]-4-cyclohexene-1,2-dicarbioximide (captafol)

3-(3,5-dichlorophenyl)-N-(1-methyl-ethyl)-2,4-dioxo-1-imidazolidine carboxamide (iprodione)

3-(3,5-dichlorophenyl)-5-ethenyl-5-methyl-2,4-oxazolidinedione (vinclozolin)

2,6-dimethyl-4-tridecylmorpholine (tridemorph) kasugamycin

O-ethyl S,S-diphenyl phosphorodithioate (edifenphos)

Bactericides:

tribasic copper sulfate

streptomycin sulfate

oxytetracycline

Acaricides:

senecioic acid, ester with 2-sec-butyl-4,6-dinitrophenol (binapacryl)

6-methyl-1,3-dithiolo[2,3-β]quinonolin-2-one (oxythioquinox)

2,2,2-trichloro-1,1-bis(4-chlorophenyl)ethanol (dicofol)

bis(pentachloro-2,4-cyclopentadien-1-yl) (dienochlor)

tricyclohexyltin hydroxide (cyhexatin)

hexakis(2-methyl-2-phenylpropyl)distannoxane (fenbutin oxide)

Nematicides:

2-[diethoxyphosphinylimino]-1,3-dithietane (fosthietan)

S-methyl-1-(dimethylcarbamoyl)-N-(methylcarbamoyloxy)thioformimidate (oxamyl)

S-methyl-1-carbamoyl-N-(methylcarbamoyloxy)thioformimidate

N-isopropylphosphoramidic acid, O-ethyl-O'-[4-(methylthio)-m-tolyl]diester (fenamiphos)

Insecticides:

3-hydroxy-N-methylcrotonamide(dimethylphosphate)ester (monocrotophos)

methylcarbamic acid, ester with 2,3-dihydro-2,2-dimethyl-7-benzofuranol (carbofuran)

O-[2,4,5-trichloro-α-(chloromethyl)benzyl]phosphoric acid, O',O'-dimethyl ester (tetrachlorvinphos)

2-mercaptosuccinic acid, diethyl ester, S-ester with thionophosphoric acid, dimethyl ester (malathion)

phosphorothioic acid, O,O-dimethyl, O-p-nitrophenyl ester (methyl parathion)

methylcarbamic acid, ester with α-naphthol (carbaryl)

methyl N-[[(methylamino)carbonyl]oxy]ethanimidothioate (methomyl)

N'-(4-chloro-o-tolyl)-N,N-dimethylformamidine (chlordimeform)

O,O-diethyl-O-(2-isopropyl-4-methyl-6-pyrimidyl)phosphorothioate (diazinon)

octachlorocamphene (toxaphene)

O-ethyl O-p-nitrophenyl phenylphosphonothioate (EPN)

cyano(3-phenoxyphenyl)-methyl 4-chloro-α-(1-methylethyl)benzeneacetate (fenvalerate)

(3-phenoxyphenyl)methyl (±)-cis,trans-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate (permethrin)

dimethyl N,N'-[thiobis](N-methylimino)carbonyloxy]]bis[ethanimidothioate] (thiodicarb)

phosphorothiolothionic acid, O-ethyl-O-[4-(methylthio)phenyl]-S-n-propyl ester (sulprofos)

α-cyano-3-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane carboxylate (cypermethrin)

cyano(3-phenoxyphenyl)methyl 4-(difluoromethoxy)-α-(methylethyl)benzeneacetate ("Payoff")

O,O-diethyl-O-(3,5,6-trichloro-2-pyridyl)phosphorothioate (chlorpyrifos)

O,O-dimethyl-S-[(4-oxo-1,2,3-benzotriazin-3-(4H)-yl)methyl]phosphorodithioate (azinphos-methyl)

5,6-dimethyl-2-dimethylamino-4-pyrimidinyl dimethyl carbamate ("Pirimor")

S-(N-formyl-N-methylcarbamoylmethyl-O,O-dimethyl phosphorodithioate (formothion)

S-2-(ethylthioethyl)-O,O-dimethyl phosphiorothioate (demeton-S-methyl)

α-cyano-3-phenoxybenzyl cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropane carboxylate (deltamethrin)

cyano(3-phenoxyphenyl)methyl ester of N-(2-chloro-4-trifluoromethylphenyl)alanine (fluvalinate)

trans-5-(4-chlorophenyl)-N-cyclohexyl-4-methyl-2-oxothiazolidine-3-carboxamide (hexythiazox)

Application

Disease control is ordinarily accomplished by applying an effective amount of the compound, normally as part of a formulation containing it, either pre- or post-infection to the portion of the plant to be protected, such as the roots, stems, foliage, fruit, seeds, tubers or bulbs, or to the medium (soil or sand) in which the plants to be protected are growing. The compound may also be applied to the seed from which the plants to be protected are to be grown.

Rates of application for these compounds can be influenced by many factors of the environment and should be determined under actual use conditions. Nevertheless, foliage can normally be protected when treated at a rate of from 1 gram or less up to 5000 grams of active ingredient per hectare. Plants growing in soil that is treated at a concentration from about 0.1 to about 20 kg of active ingredient per hectare can be protected from disease. Seed and seedlings can normally be protected when seed is treated at a rate of from about 0.06 to about 3 grams of active ingredient per kilogram of seed.

In the following Examples 22-34, the percent disease control is determined as the percent growth inhibition of colonies on treated plants as compared to untreated plants. Results for Examples 22-34 are given in Table VI. In the table, a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control relative to the controls. A "-" entry indicates that no test was performed with the specified compound. The number of the test compound corresponds to the similarly numbered compound in Tables I-V.

EXAMPLE 22

The test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on apple seedlings. The following day plants were inoculated with a spore suspension of Venturia inaequalis, the causal agent of apple scab, and incubated in a saturated humidity chamber at 20° C. for 24 hours and then in a growth chamber at 22° C. for 11 days, when disease ratings were made.

EXAMPLE 23

The test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on peanut seedlings. The following day plants were inoculated with a spore suspension of Cercosporidium personatum, the causal agent of Peanut Late Leafspot, and incubated in a saturated humidity chamber at 22° C. for 24 hours and then in a high humidity chamber at 27° C. for 7 days, and then in a growth chamber at 29° C. for 7 days, when disease ratings were made.

EXAMPLE 24

The test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on broad bean seedlings. The following day plants were inoculated with a spore suspension of Botrytis cinerea, the causal agent of bean grey mold, and incubated in a saturated humidity chamber at 20° C. for 24 hours when disease ratings were made.

EXAMPLE 25

The test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on wheat seedlings. The following day plants were inoculated with a spore dust of Erysiphe graminis f. sp. tritici, the causal agent of wheat powdery mildew, and incubated in a saturated humidity chamber at 20° C. for 6 days when disease ratings were made.

EXAMPLE 26

The test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on rice seedlings. The following day plants were inoculated with a spore suspension of Pyricularia oryzae, the causal agent of rice blast, and incubated in a saturated humidity chamber at 27° C. for 24 hours and then in a growth chamber at 29° C. for 4 days, when disease ratings were made.

EXAMPLE 27

The test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on rice seedlings. The following day plants were inoculated with a spore suspension of Rhizoctonia solani, the causal agent of rice sheath blight, and incubated in a saturated humidity chamber at 27° C. for 48 hours and then in a growth chamber at 29° C. for 4 days, when disease ratings were made.

EXAMPLE 28

The test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on wheat seedlings. The following day plants were inoculated with a spore suspension of Puccinia recondita, the causal agent of wheat leaf rust, and incubated in a saturated humidity chamber at 20° C. for 24 hours and then in a growth chamber at 20° C. for 8 days, when disease ratings were made.

EXAMPLE 29

The test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on tomato seedlings. The following day plants were inoculated with a spore suspension of Phytophthora infestans, the causal agent of tomato late blight, and incubated in a saturated humidity chamber at 20° C. for 24 hours and then in a growth chamber at 20° C. for 5 days, when disease ratings were made.

EXAMPLE 30

The test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on grape seedlings. The following day plants were inoculated with a spore suspension of Plasmorpara viticola, the causal agent of grape downy mildew, and incubated in a saturated humidity chamber at 20° C. for 24 hours and then in a growth chamber at 20° C. for 7 days and then held in a saturated humidity chamber at 20° C. for 24 hours, when disease ratings were made.

EXAMPLE 31

The test compounds were dissolved in acetone so that 1 ml of solution yielded a concentration of 0.5 kilogram/hectare when added to cucumber seeds and soil in pots. Seeds and soil were then inoculated with a mixture of sand, cereal and mycelium of the fungus Pythium aphanadermatum, causal agent of cucumber damping off, and incubated in a growth chamber at 30° C. for 14 days. Disease ratings were then made.

EXAMPLE 32

The test compounds were dissolved in acetone so that 1 ml of solution yielded a concentration of 0.5 kilogram/hectare when added to cotton seeds and soil in pots. Seeds and soil were then inoculated with a mixture of sand, cereal and mycelium of the fungus Rhizoctonia solani, causal agent of cotton blight, and incubated in a growth chamber at 30° C. for 14 days. Disease ratings were then made.

EXAMPLE 33

The test compounds were dissolved in acetone so that 1 ml of solution yielded a concentration of 0.5 kilogram/hectare when added to cucumber seeds and soil in pots. Seeds and soil were then inoculated with a mixture of sand, cereal and mycelium of the fungus Fusarium oxysporum f. sp. cucumerinum, causal agent of cucumber wilt, and incubated in a growth chamber at 30° C. for 14 days. Disease ratings were then made.

EXAMPLE 34

The test compounds were dissolved in acetone so that 1 ml of solution yielded a concentration of 0.5 kilogram/hectare when added to lima bean seeds and soil in pots. Seeds and soil were then inoculated with a mixture of sand, cereal and mycelium of the fungus Sclerotium rolfsii, causal agent of southern blight, and incubated in a growth chamber at 30° C. for 14 days. Disease ratings were then made.

                                      TABLE VI                                     __________________________________________________________________________     PLANT DISEASE CONTROL DATA                                                     Cmpd                                                                               EX.                                                                               EX.                                                                               EX.                                                                               EX.                                                                               EX.                                                                               EX.                                                                               EX.                                                                               EX.                                                                               EX.                                                                               EX.                                                                               EX.                                                                               EX.                                                                               EX.                                    No. 22 23 24 25 26 27 28 29 30 31 32 33 34                                     __________________________________________________________________________     30  100                                                                               89 43 84 0  0  38 0  0  0  0  0  0                                      5   90 95 90 61 0  0  46 0  98 0  0  50 0                                      46  41 53 93 86 2  0  48 26 77 0  0  0  0                                      90  0  92 90 55 51 0  0  0  0  0  0  0  0                                      45  77 75 38 94 20 0  0  0  92 0  0  0  0                                      91  77 0  86 84 0  0  0  0  59 0  0  0  0                                      8   80 0  80 -- 0  0  100                                                                               0  -- -- -- -- --                                     9   100                                                                               -- 0  -- 80 90 100                                                                               0  -- -- -- -- --                                     10  100                                                                               -- 0  -- 80 0  90 0  -- -- -- -- --                                     12  -- 95 41 100                                                                               28 0  47 0  0  0  0  0  0                                      15  -- 75 0  93 0  0  0  0  -- 0  0  0  0                                      13  -- 73 56 100                                                                               36 0  11 81 37 0  0  0  0                                      14  -- 2  56 80 36 0  0  0  37 0  0  0  0                                      16  -- 0  56 100                                                                               0  0  11 26 0  0  0  0  0                                      17  -- 47 27 93 0  0  0  81 0  0  0  0  0                                      23  75 98 72 91 3  0  90 0  26 0  0  0  0                                      29  97 100                                                                               54 57 3  62 48 0  0  0  0  0  0                                      27  100                                                                               98 54 74 3  0  48 0  0  0  0  0  0                                      28  97 100                                                                               90 91 3  73 77 0  0  0  0  0  0                                      63  53 98 54 29 0  0  0  0  86 0  0  0  0                                      67  95 88 30 100                                                                               52 28 58 30 100                                                                               0  0  0  0                                      55  100                                                                               49 38 90 34 8  0  0  15 0  0  0  0                                      2   81 100                                                                               63 100                                                                               34 8  0  -- 15 0  0  0  0                                      6   100                                                                               100                                                                               74 100                                                                               70 32 96 0  12 0  0  0  0                                      21  72 96 65 58 63 0  23 0  59 0  0  0  0                                      40  100                                                                               96 65 98 0  19 85 0  16 0  0  0  0                                      24  100                                                                               82 63 82 45 0  54 0  12 0  0  0  0                                      25  100                                                                               95 84 100                                                                               49 33 63 0  41 0  0  0  0                                      26  100                                                                               100                                                                               84 100                                                                               49 48 63 0  18 0  0  0  0                                      50  100                                                                               91 91 94 90 16 63 0  0  0  0  0  0                                      49  100                                                                               91 91 94 49 16 63 0  18 0  0  0  0                                      42  100                                                                               96 75 85 44 86 61 0  42 0  0  0  0                                      52  100                                                                               100                                                                               91 98 89 57 61 21 60 0  0  0  0                                      53  100                                                                               92 75 95 44 57 61 0  19 0  0  0  0                                      54  100                                                                               96 85 85 0  42 12 0  0  0  0  0  0                                      43  100                                                                               100                                                                               98 95 86 16 66 23 86 0  0  0  0                                      39  100                                                                               98 96 86 97 16 66 0  74 0  0  0  0                                      41  100                                                                               98 94 91 86 16 66 0  0  0  0  0  0                                      44  100                                                                               98 94 91 31 0  66 0  56 0  0  0  0                                      73  93 52 53 76 31 0  24 0  0  0  0  0  0                                      72  100                                                                               85 53 76 86 0  24 0  0  0  0  0  0                                      62  93 96 94 86 97 0  66 0  94 0  0  0  0                                      66  40 66 67 95 0  0  0  0  85 0  0  0  0                                      65  40 28 80 95 0  0  0  0  20 0  0  0  0                                      69  0  100                                                                               0  98 19 0  3  0  20 0  0  0  0                                      71  62 93 9  98 19 0  3  0  20 0  0  0  0                                      76  77 93 80 95 19 0  3  0  0  0  0  0  0                                      4   100                                                                               100                                                                               9  98 19 19 91 0  0  0  0  0  0                                      64  40 66 67 37 19 0  3  0  0  0  0  0  0                                      75  98 100                                                                               45 95 19 0  56 0  20 0  0  0  0                                      93  68 89 47 75 0  0  83 0  21 0  0  0  0                                      92  0  49 81 32 0  0  61 0  0  0  0  0  0                                      94  68 0  93 32 0  0  61 0  92 0  0  0  0                                      95  75 58 0  32 30 0  44 0  0  0  0  0  0                                      56  20 75 62 57 0  13 0  0  20 0  0  0  0                                      68  0  75 62 74 49 0  0  0  97 0  0  0  0                                      11  100                                                                               100                                                                               100                                                                               92 0  0  50 0  0  0  0  0  0                                      96  94 0  87 29 0  0  16 26 99 0  0  0  0                                      74  100                                                                               100                                                                               81 100                                                                               0  32 91 0  7  0  0  0  0                                      1   73 95 87 84 18 0  72 0  0  0  0  0  0                                      89  40 18 54 83 31 0  80 0  21 0  0  0  0                                      70  72 97 11 48 0  0  4  0  100                                                                               0  0  0  0                                      58  53 97 11 14 0  0  4  0  98 0  0  0  0                                      88  85 100                                                                               97 43 78 0  63 0  21 0  0  0  0                                      86  85 100                                                                               85 79 50 0  93 0  0  0  0  0  0                                      20  100                                                                               100                                                                               97 43 0  0  18 0  79 0  70 0  0                                      22  100                                                                               100                                                                               91 95 78 0  100                                                                               0  65 0  0  60 0                                      79  72 67 32 79 50 0  63 0  65 0  60 80 0                                      78  98 100                                                                               85 92 0  0  18 0  79 0  0  0  0                                      85  85 97 93 81 0  0  57 0  0  0  0  0  0                                      87  98 100                                                                               96 96 0  33 89 0  49 0  0  0  0                                      84  100                                                                               100                                                                               89 100                                                                               52 33 89 0  49 0  0  0  0                                      80  94 93 66 97 0  0  0  0  0  0  0  0  0                                      81  100                                                                               100                                                                               88 100                                                                               0  0  0  0  22 0  0  0  0                                      82  100                                                                               100                                                                               0  50 0  0  0  0  21 0  0  0  0                                      83  100                                                                               95 0  50 0  0  0  0  21 0  0  0  0                                      77  71 100                                                                               74 100                                                                               28 18 86 0  33 0  0  0  0                                      60  83 97 86 100                                                                               61 35 29 0  16 0  70 0  0                                      59  17 93 78 85 46 18 29 0  59 0  0  0  0                                      18  68 97 78 100                                                                               0  0  29 0  16 0  0  0  0                                      31  83 84 92 31 46 0  0  0  84 0  0  0  0                                      34  83 97 86 98 46 0  0  0  16 100                                                                               0  0  0                                      35  83 84 86 98 46 0  0  0  0  0  0  0  0                                      38  68 97 78 94 46 0  29 0  0  0  0  0  0                                      36  68 7  71 92 44 0  7  0  0  0  0  0  0                                      37  100                                                                               91 71 77 0  0  58 0  0  0  0  0  0                                      19  100                                                                               100                                                                               82 92 0  0  58 0  45 0  0  0  0                                      61  100                                                                               100                                                                               71 86 0  0  58 0  0  0  60 0  0                                      57  68 81 82 77 0  0  58 0  0  0  0  0  0                                      48  100                                                                               100                                                                               82 95 0  0  81 0  0  0  0  0  0                                      7   100                                                                               100                                                                               94 100                                                                               0  0  58 0  0  0  0  60 0                                      32  83 91 96 61 0  0  7  0  0  0  0  0  0                                      33  98 100                                                                               20 92 0  0  7  0  0  0  0  0  0                                      47  100                                                                               100                                                                               82 95 0  0  58 0  0  0  0  0  0                                      51  100                                                                               100                                                                               89 100                                                                               0  0  58 0  0  0  0  0  0                                      3   0  50 0  -- 0  0  0  0  -- 6  0  0  6                                      97  91 98 81 92 42 62 91 23 62 0  0  0  0                                      98  100                                                                               60 91 96 0  71 0  25 33 0  0  0  0                                      99  53 98 91 97 63 0  36 0  52 0  0  0  0                                      __________________________________________________________________________ 

What is claimed:
 1. A compound of the general formula: ##STR295## wherein R₁ is ##STR296## naphthyl, --CR₇ ═CHR₈, or --C.tbd.CR₇ : R₂ and R₃ are independently C₁ -C₆ alkyl, vinyl, CH₂ CR₉ ═CR₁₀ R₁₁, ##STR297## or OR₁₂ provided that both R₂ and R₃ may not be OR₁₂ :R₄ is H or CH₃ : R₅ and R₆ are independently H, F, Cl, Br, OCH₃, SCH₃, OCF₂ H, OCF₃, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, phenyl, or halophenyl: R₇ and R₈ are independently H, C₁ -C₄ alkyl, or ##STR298## R₉, R₁₀ and R₁₁ are independently H or CH₃ ; Z is N or CH;when Z is N, X is H, C₂ -C₄ alkenyl, ethynyl, F, Cl, Br, I, NO₂, SH and its corresponding disulfide, SeH and its corresponding diselenide, ##STR299## Y is H, F, Cl, Br, I, ##STR300## SSR₁₇, CO₂ CH₃, CHO, or SH and its corresponding disulfide; m is 0 or 1; n is 0, 1, or 2; R₁₂ is H or C₁ -C₄ alkyl; R₁₃ is H, C₁ -C₄ alkyl, allyl, benzyl, C₁ -C₄ alkylcarbonyl, C₁ -C₄ haloalkylcarbonyl; R₁₄ and R₁₅ are independently H, C₁ -C₄ alkyl, allyl, benzyl, or phenyl optionally substituted with 1-3 substituents independently selected from halogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, NO₂ or SCH₃ ; R₁₆ is H, C₁ -C₈ alkyl, C₃ -C₈ cycloalkyl, C₂ -C₈ alkenyl, C₄ -C₈ cycloalkenyl, alpha-pinenyl, aralkyl, aralkenyl, or phenyl optionally substituted with 1-3 substituents independently selected from halogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, NO₂ or SCH₃ ; R₁₇ is C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, allyl, benzyl or phenyl optionally substituted with 1-3 substituents independently selected from halogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, NO₂ or SCH₃ ; R₁₈ is C₁ -C₅ alkyl, C₁ -C₄ haloalkyl, CH₂ SCN, C₂ -C₄ alkenyl, CHR₉ (CHR₁₀)_(m) CN, CH₂ CO₂ R₁₄, C₃ -C₄ alkynyl, CH₂ NO₂, benzyl, CH₂ OCH₃, ##STR301## R₁₉ is CH₃, phenyl, or benzyl; R₂₀ is C₁ -C₄ alkyl, CH₂ CN, CH₂ SCN, or allyl; provided that either X or Y must be H but both X and Y cannot be H simultaneously; when Z is CH, Y is H and X is S(O)_(n) R₂₁, SO₂ OH, I or SH and its corresponding disulfide; R₂₁ is C₂ -C₄ alkyl, CH₂ CN or CH₂ SCN.
 2. The compound of claim 1 wherein ##STR302## R₅ and R₆ are independently H, F, Cl, Br, phenyl, or halophenyl; R₂ is C₁ -C₄ alkyl or ##STR303## R₃ is C₁ -C₄ alkyl, vinyl, allyl, or OR₁₂ ; R₄ is H;X is F, Cl, I, ##STR304## SSR₁₇, or SH and its corresponding disulfide; and Y is H.
 3. The compound of claim 2 whereinR₃ is C₁ -C₄ alkyl, allyl, or OR₁₂ ; R₅ and R₆ are independently H, F, Cl, Br, phenyl, or halophenyl substituted at the 4-position; and X is I, ##STR305## SSR₁₇, or SH and its corresponding disulfide.
 4. The compound of claim 3 whereinX is I, ##STR306## SSR₁₇, or SH and its corresponding disulfide.
 5. The compound of claim 1 which is 1-[bis(4-fluorophenyl)(methyl)silylmethyl]-1H-1,2,4-triazole-5-thiol.
 6. The compound of claim 1 which is 1-[bis(4-fluorophenyl)(methyl)silylmethyl]-5-iodo-1H-1,2,4-triazole.
 7. The compound of claim 1 which is 1-[bis(4-fluorophenyl)(methyl)silylmethyl]-5-(cyanomethylsulfonyl)-1H-1,2,4-triazole.
 8. The compound of claim 1 which is 1-[bis(4-fluorophenyl)(methyl)silylmethyl]-2-iodo-1H-imidazole.
 9. A composition for controlling fungus disease which comprises an effective amount of a compound of claim 1 and at least one of the following: surfactant, solid or liquid inert diluent.
 10. A composition for controlling fungus disease which comprises an effective amount of a compound of claim 2 and at least one of the following: surfactant, solid or liquid inert diluent.
 11. A composition for controlling fungus disease which comprises an effective amount of a compound of claim 3 and at least one of the following: surfactant, solid or liquid inert diluent.
 12. A composition for controlling fungus disease which comprises an effective amount of a compound of claim 4 and at least one of the following; surfactant, solid or liquid inert diluent.
 13. A composition for controlling fungus disease which comprises an effective amount of a compound of claim 5 and at least one of the following: surfactant, solid or liquid inert diluent.
 14. A composition for controlling fungus disease which comprises an effective amount of a compound of claim 6 and at least one of the following: surfactant, solid or liquid inert diluent.
 15. A composition for controlling fungus disease which comprises an effective amount of a compound of claim 7 and at least one of the following: surfactant, solid or liquid inert diluent.
 16. A composition for controlling fungus disease which comprises an effective amount of a compound of claim 8 and at least one of the following: surfactant, solid or liquid inert diluent.
 17. A method for controlling fungus disease which comprises applying to the locus of infestation to be protected an effective amount of a compound of claim
 1. 18. A method for controlling fungus disease which comprises applying to the locus of infestation to be protected an effective amount of a compound of claim
 2. 19. A method for controlling fungus disease which comprises applying to the locus of infestation to be protected an effective amount of a compound of claim
 3. 20. A method for controlling fungus disease which comprises applying to the locus of infestation to be protected an effective amount of a compound of claim
 4. 21. A method for controlling fungus disease which comprises applying to the locus of infestation to be protected an effective amount of a compound of claim
 5. 22. A method for controlling fungus disease which comprises applying to the locus of infestation to be protected an effective amount of a compound of claim
 6. 23. A method for controlling fungus disease which comprises applying to the locus of infestation to be protected an effective amount of a compound of claim
 7. 24. A method for controlling fungus disease which comprises applying to the locus of infestation to be protected an effective amount of a compound of claim
 8. 